CN104798156A - Photoelectric conversion element, dye-sensitized solar cell, metal complex dye, dye solution, dye-adsorbed electrode, and method for manufacturing dye-sensitized solar cell - Google Patents

Photoelectric conversion element, dye-sensitized solar cell, metal complex dye, dye solution, dye-adsorbed electrode, and method for manufacturing dye-sensitized solar cell Download PDF

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CN104798156A
CN104798156A CN201380060506.5A CN201380060506A CN104798156A CN 104798156 A CN104798156 A CN 104798156A CN 201380060506 A CN201380060506 A CN 201380060506A CN 104798156 A CN104798156 A CN 104798156A
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CN104798156B (en
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渡辺康介
谷征夫
佐佐木晃逸
佐藤宽敬
纲和宏
小林克
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Fujifilm Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2059—Light-sensitive devices comprising an organic dye as the active light absorbing material, e.g. adsorbed on an electrode or dissolved in solution
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/55—Acids; Esters
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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/54—Radicals substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
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    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
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    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
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    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0046—Ruthenium compounds
    • C07F15/0053—Ruthenium compounds without a metal-carbon linkage
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B19/00—Oxazine dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B21/00—Thiazine dyes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/0008—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain
    • C09B23/005—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain the substituent being a COOH and/or a functional derivative thereof
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/0008—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain
    • C09B23/005—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain the substituent being a COOH and/or a functional derivative thereof
    • C09B23/0058—Methine or polymethine dyes, e.g. cyanine dyes substituted on the polymethine chain the substituent being a COOH and/or a functional derivative thereof the substituent being CN
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B23/00—Methine or polymethine dyes, e.g. cyanine dyes
    • C09B23/10—The polymethine chain containing an even number of >CH- groups
    • C09B23/105—The polymethine chain containing an even number of >CH- groups two >CH- groups
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B57/00—Other synthetic dyes of known constitution
    • C09B57/008—Triarylamine dyes containing no other chromophores
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09B57/00—Other synthetic dyes of known constitution
    • C09B57/10—Metal complexes of organic compounds not being dyes in uncomplexed form
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B69/00—Dyes not provided for by a single group of this subclass
    • C09B69/008—Dyes containing a substituent, which contains a silicium atom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
    • H10K85/344—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising ruthenium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/20—Light-sensitive devices
    • H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
    • H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/542—Dye sensitized solar cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

A photoelectric conversion element which comprises a conductive supporting body, a photosensitive layer containing an electrolyte, a charge transfer layer containing an electrolyte, and a counter electrode, and wherein the photosensitive layer contains fine semiconductor particles that are loaded with a metal complex dye represented by formula (I); a metal complex dye; a dye solution; a dye-adsorbed electrode; a dye-sensitized solar cell; and a method for manufacturing the dye-sensitized solar cell. M(LA)(LD)(LX)mX*(CI)mY formula (I) In formula (I), M represents a metal ion; LA represents a tridentate ligand represented by formula (AL); LD represents a bidentate or tridentate ligand wherein at least one coordinating atom is an anion; LX represents a monodentate ligand; CI represents a counter ion; mX represents 0 or 1; and mY represents an integer of 0-3. formula (AL) In formula (AL), each of rings A-C represents a nitrogen-containing aromatic hetero ring; each of Z1 and Z2 represents a carbon atom or a nitrogen atom; each of Anc1-Anc3 represents an acidic group; each of X1 and X3 represents a single bond or a linking group; X2 represents a linking group that is linked in a conjugated form or a single bond, and in cases where X2 is a linking group, the linking group contains an ethenylene group, an ethynylene group, an arylene group or a heteroarylene group in a linking chain; each of R1-R3 represents a substituent; each of l1 and l3 represents an integer of 1-4; l2 represents an integer of 1-5; each of m1 and m3 represents an integer of 0-4; m2 represents an integer of 1-3; each of n1 and n2 represents an integer of 0-3; and n3 represents an integer of 0-4. In cases where X2 is a single bond, m1 or m3 represents an integer of 1-4 and X1 or X3 represents a linking group.

Description

The manufacture method of photo-electric conversion element, dye-sensitized solar cell, metal complex dye, pigment solution, pigment adsorption electrode and dye-sensitized solar cell
Technical field
The present invention relates to the manufacture method of a kind of photo-electric conversion element, dye-sensitized solar cell, metal complex dye, pigment solution, pigment adsorption electrode and dye-sensitized solar cell.
Background technology
Photo-electric conversion element is used in various optical sensor (photosensor), photocopier (copying machine), solar cell (solar cell) etc.In this photo-electric conversion element, by use metal, use semiconductor, use organic pigment or pigment or they are combined etc. various mode in addition practical.Especially utilizing the solar cell of the solar energy of non-exhaustion not need fuel, rather expecting its regular practicality as utilizing the element of endless clean energy (clean energy).Wherein, always silicon system solar cell researchs and develops since ancient times, also advancing universal because of the policy consideration of various countries.But silicon is inorganic material, in the improvement of output (throughput) and cost (cost) etc., have the limit by oneself.
Therefore, the research of dye-sensitized solar cell is being concentrated one's energy to carry out.Especially the achievement in research of the people such as Gray Ce Er (Graetzel) of Switzerland (Swiss) Lausanne (Lausanne) college of engineering becomes the favourable turn of above-mentioned research.The people such as Gray Ce Er adopt fixed packet on the surface of porous (porous) thin film of titanium oxide containing the structure of the pigment of ruthenium complex, to achieve the conversion efficiency equal with amorphous silicon.Thus, even if the dye-sensitized solar cell one not using expensive vacuum plant also can manufacture jumps and receives the concern of whole world researcher.
Up to now, as the metal complex dye used in photo-electric conversion element, usually have developed the pigment etc. being called as N3, N719, Z907, J2.
On the other hand, in order to utilize the light of the wavelength of light in the wave-length coverage of more than 800nm or visible, infra-red range, carrying out the kind of absorption base to semiconductive particles sub-surface or the research of introduction method, proposing: via ethenylidene (ethenylene), the absorption base as acidic groups is being directed into (with reference to patent documentation 1) on pyridine ring; Or make replacement on 2 have the vinyl (ethenyl) of acidic groups and specific electron-withdrawing base to be binding on chromophore (with reference to patent documentation 2) via conjugated system.But, for the raising of photoelectric conversion efficiency and durability, may not meet the demands.
[prior art document]
[patent documentation]
[patent documentation 1] Japanese Patent Laid-Open 2002-105346 publication
[patent documentation 2] Japan Patent spy table 2011-502187 publication
Summary of the invention
Invent problem to be solved
In view of above-mentioned condition, problem of the present invention is to provide a kind of photo-electric conversion element, dye-sensitized solar cell, it makes the light absorption of long wavelength range increase in the absorption characteristic of metal complex dye, spectral sensitivity characteristic in this long wavelength range is improved, thus make photoelectric conversion efficiency improve, and to the absorption stability of semiconductive particles sub-surface or excellent in te pins of durability.In addition, problem of the present invention is to provide a kind of manufacture method of the metal complex dye, pigment solution, pigment adsorption electrode and the dye-sensitized solar cell that are suitably used for above-mentioned photo-electric conversion element and dye-sensitized solar cell.
The technological means of dealing with problems
The spectral sensitivity characteristic of existing pigment in long wavelength range may not be abundant, therefore various research has been carried out in the raising of the people such as the present inventor to the spectral sensitivity characteristic in long wavelength range, i.e. quantum yield (electricity conversion (Incident Photon-to-electron Conversion Efficiency, IPCE)).On the other hand, for the metal complex dye through ligands such as such nitrogen-containing hetero aromatic ring, the such as bipyridines of pyridine ring, in order to improve the spectral sensitivity characteristic in long wavelength range, the part attempted not having the function being adsorbed in semiconductor microactuator particle surface changes.But the raising of the raising and durability that realize photoelectric conversion efficiency has very large obstacle simultaneously.Therefore, from different in the past, the spectral sensitivity characteristic that the chemical constitution having the part of the function being adsorbed in semiconductor microactuator particle surface by change improves in long wavelength range is studied, and then, various research is also carried out to the part without the function being adsorbed in semiconductor microactuator particle surface, and have studied the raising of further long wavelengthization, absorption stability or durability.Found that, with regard to the long wavelengthization of the expansion gained of the conjugated system by part and the viewpoint of absorption property or durability, structure importantly near various absorption base, absorption base are to the link of nitrogen-containing hetero aromatic ring or substitution technique, and importantly with the combination of bidentate ligand or tridentate ligand, thus complete the present invention.
That is, problem of the present invention is realized by following means.
(1) a kind of photo-electric conversion element, there is conductive support body, containing electrolytical photoreceptor layers, containing electrolytical Charger transfer body layer and to electrode, and photoreceptor layers contains the semiconductor microactuator particle of the metal complex dye carried represented by following formula (I)
M (LA) (LD) (LX) mX(CI) mYformula (I)
[in formula, M represents metal ion;
LA represents the tridentate ligand represented by following formula (AL);
LD represents bidentate ligand or the tridentate ligand different from LA; Herein, in this bidentate ligand or this tridentate ligand is anion with at least one of the coordination atom of metal ions M bond;
LX represents monodentate ligand; MX represents 1 when LD is bidentate ligand, represents 0 when LD is tridentate ligand;
CI represent must gegenion to make the gegenion during situation of charging neutrality;
MY represents the integer of 0 ~ 3];
[changing 1]
[in formula, ring A, ring B and ring C separately represent nitrogenous heteroaromatic; Herein, Z 1and the key between atom N and Z 2and the key between atom N can be singly-bound and also can be double bond; Z 1and Z 2separately represent carbon atom or nitrogen-atoms;
Anc1 ~ Anc3 separately represents acidic groups; L1 and l3 separately represents the integer of 1 ~ 4, and l2 represents the integer of 1 ~ 5.
X 1and X 3separately represent singly-bound or concatenating group, X 2for with the X of at least one Anc2 institute bond of pi-conjugated link 2atom and the concatenating group of nitrogenous heteroaromatic of ring B or singly-bound, and when the situation for concatenating group in its coupling chain containing ethenylidene, ethynylene, arlydene or inferior heteroaryl; X 1with ring A, X 2with ring B, X 3also can bond and form contracting ring with ring C; M1 and m3 separately represents the integer of 0 ~ 4, and m2 represents the integer of 1 ~ 3; At X 2during situation for singly-bound, m1 or m3 represents the integer of 1 ~ 4, and X 1or X 3represent concatenating group;
R 1~ R 3separately represent the substituting group without Anc1 ~ Anc3; N1 and n2 separately represents the integer of 0 ~ 3, and n3 represents the integer of 0 ~ 4; At R 1~ R 3each when there is multiple situations respectively, they also can mutually bond and form ring].
(2) according to the photo-electric conversion element described in (1), wherein M is Os 2+or Ru 2+.
(3) according to (1) or the photo-electric conversion element described in (2), wherein X 2be separately any one or group that they are combined of singly-bound or following formula (X-1) ~ formula (X-6),
[changing 2]
[in formula, Q 1represent and be selected from-S-,-O-,-N (R xA)-,-C (R xB) (R xC)-and-Si (R xB) (R xC)-in group; Herein, R xA~ R xCseparately represent hydrogen atom or substituting group; In addition, R xBwith R xCalso can bond and form ring mutually; R x1~ R x9separately represent hydrogen atom or substituting group; Herein, R x1with R x2, R x3with R x4, R x4with R x5, R x5with R xA, R x5with R xB, R x6with R x7, R x8with R x9respectively also can bond and form ring mutually; R x1~ R x4, R x6~ R x9also contracting ring can be formed with ring B bond; * represent the binding site with ring B, * * represents the binding site with Anc2].
(4) described any one of (1) to (3) photo-electric conversion element, wherein X 1and X 3at least one be separately any one or group that they are combined of following formula (X-1) ~ formula (X-6),
[changing 3]
[in formula, Q 1represent and be selected from-S-,-O-,-N (R xA)-,-C (R xB) (R xC)-and-Si (R xB) (R xC)-in group; Herein, R xA~ R xCseparately represent hydrogen atom or substituting group; In addition, R xBwith R xCalso can bond and form ring mutually; R x1~ R x9separately represent hydrogen atom or substituting group; Herein, R x1with R x2, R x3with R x4, R x4with R x5, R x5with R xA, R x5with R xB, R x6with R x7, R x8with R x9respectively also can bond and form ring mutually; R x1~ R x4, R x6~ R x9also contracting ring can be formed with ring A or ring C bond; * represent the binding site with ring A or ring C, * * represents the binding site with Anc1 or Anc3].
(5) according to (3) or the photo-electric conversion element described in (4), the R of its Chinese style (X-1) x1with R x2be hydrogen atom.
(6) according to (3) or the photo-electric conversion element described in (4), wherein X 2for the group represented by formula (X-1), R x1or R x2for alkyl or aryl.
(7) described any one of (1) to (4) and (6) photo-electric conversion element, wherein X 2in pi-conjugated part-structure, have that=C (Rz)-("=" associative key is positioned at ring B side to represented structure, and "-" associative key is positioned at Anc2 side; Herein, Rz represents that the σ p value of Hammett's rule (Hammett ' s rule) is the substituting group of more than 0.05).
(8) described any one of (1) to (4) and (7) photo-electric conversion element, wherein X 2represented by following formula (X-1A) or formula (X-2A),
[changing 4]
[in formula, Rz represents that the σ p value of Hammett's rule is the substituting group of more than 0.05; Ring X represents aromatic carbon ring base or aromatic heterocycle; Herein, the associative key on the left of paper is binding on ring B, and Anc2 is binding on the associative key on the right side of paper].
(9) described any one of (1) to (8) photo-electric conversion element, wherein X 1and X 3be separately X 2represented concatenating group.
(10) described any one of (1) to (9) photo-electric conversion element, wherein ring B is pyridine ring.
(11) described any one of (1) to (10) photo-electric conversion element, wherein ring A and ring C is separately for being selected from the ring in pyridine ring, quinoline ring, pyrimidine ring, triazine ring, imidazole ring, benzimidazole Huan, oxazole ring, thiazole ring, benzothiazole Huan, oxadiazole rings, Thiadiazole, isoxazole ring, isothiazole ring, triazole ring and pyrazole ring.
(12) described any one of (1) to (11) photo-electric conversion element, wherein ring A ~ ring C is pyridine ring.
(13) according to photo-electric conversion element described any one of (1) to (12), at least one of wherein m1 and m3 is 1, and m2 is 1.
(14) described any one of (1) to (13) photo-electric conversion element, wherein m1 ~ m3 is 1.
(15) described any one of (1) to (8) and (10) to (14) photo-electric conversion element, wherein m1 ~ m3 is 1, and X 2for singly-bound.
(16) according to photo-electric conversion element described any one of (1) to (15), the wherein LD bidentate ligand that is following formula (2L-1) ~ formula (2L-5) represented by any one,
[changing 5]
[in formula, ring D, " represent aromatic ring; A 111~ A 141separately represent nitrogen-atoms anion or carbon atom anion, A 151represent nitrogen-atoms anion, oxygen atom anion or sulphur atom anion; R 111~ R 154separately represent hydrogen atom or not there is the substituting group of Anc1, Anc2 and Anc3; Herein, * represents the binding site with metal ions M].
(17) according to photo-electric conversion element described any one of (1) to (15), the wherein LD tridentate ligand that is following formula (3L-1) ~ formula (3L-4) represented by any one,
[changing 6]
[in formula, ring D, " represent aromatic ring; A 211~ A 242separately represent nitrogen-atoms or carbon atom; Wherein, each A 211with A 212, A 221with A 222, A 231with A 232, A 241with A 242at least one be anion; R 211~ R 241separately represent hydrogen atom or not there is the substituting group of Anc1, Anc2 and Anc3; Herein, * represents the binding site with metal ions M].
(18) described any one of (1) to (17) photo-electric conversion element, wherein the bidentate ligand of above-mentioned LD or the atom being coordinated in metal ions M of tridentate ligand are nitrogen anion or carboanion, and there is following formula (SA) in part-structure
[changing 7]
[in formula, R dA1represent aryl, R dA2represent alkyl or aryl; R dA1with R dA2also can bond and form ring mutually; LL represents vinyl, acetenyl, arlydene or inferior heteroaryl; A represents the integer of 0 ~ 5].
(19) described any one of (1) to (18) photo-electric conversion element, its Chinese style (I) is represented by following formula (I-1) or formula (I-2),
[changing 8]
[in formula, M and LX in M and LX and formula (I) is synonymous, Anc1 ~ Anc3, X 1~ X 3, l1 ~ l3, m1 ~ m3, R 1~ R 3, Anc1 ~ Anc3, X in n1 ~ n3 and formula (AL) 1~ X 3, l1 ~ l3, m1 ~ m3, R 1~ R 3, n1 ~ n3 is synonymous;
Ring D and ring E separately represents the aromatic ring of 5 rings or 6 rings; D 1and D 2separately represent hydrogen atom to dissociate and be binding on the carbon atom of M or hydrogen atom dissociates and is binding on the nitrogen-atoms of M; Herein, the D in ring D and ring E 1and D 2and with the key between the carbon atom of pyridine ring bond can be singly-bound and also can be double bond;
R a1~ R a4separately represent substituting group; Ma1, ma2 and ma4 separately represent the integer of 0 ~ 3; Ma3 represents the integer of 0 ~ 4;
When ma1 ~ ma4 is respectively the integer of more than 2, multiple R a1~ multiple R a4also can mutually bond and form ring].
(20) according to photo-electric conversion element described in (19), the ring D in its Chinese style (I-1) or formula (I-2) and ring E is separately pyrazole ring, triazole ring or phenyl ring.
(21) described any one of (1) to (20) photo-electric conversion element, wherein carries the coadsorbent with more than one acidic groups further on semiconductor microactuator particle.
(22) according to the photo-electric conversion element described in (21), wherein coadsorbent is represented by following formula (CA);
[changing 9]
[in formula, R a1represent the substituting group with acidic groups; R a2represent substituting group; NA represents the integer of more than 0].
(23) a dye-sensitized solar cell, possesses photo-electric conversion element described any one of above-mentioned (1) to (22).
(24) metal complex dye, it is represented by following formula (I),
M (LA) (LD) (LX) mX(CI) mYformula (I)
[in formula, M represents metal ion;
LA represents the tridentate ligand represented by following formula (AL);
LD represents bidentate ligand or the tridentate ligand different from this LA; Herein, in this bidentate ligand or this tridentate ligand is anion with at least one of the coordination atom of metal ions M bond;
LX represents monodentate ligand; MX represents 1 when LD is bidentate ligand, represents 0 when LD is tridentate ligand;
CI represent must gegenion to make the gegenion during situation of charging neutrality;
MY represents the integer of 0 ~ 3];
[changing 10]
[in formula, ring A, ring B and ring C separately represent nitrogenous heteroaromatic; Herein, Z 1and the key between atom N and Z 2and the key between atom N can be singly-bound and also can be double bond; Z 1and Z 2separately represent carbon atom or nitrogen-atoms;
Anc1 ~ Anc3 separately represents acidic groups; L1 and l3 separately represents the integer of 1 ~ 4, and l2 represents the integer of 1 ~ 5;
X 1and X 3separately represent singly-bound or concatenating group, X 2for with the X of at least one Anc2 institute bond of pi-conjugated link 2atom and the concatenating group of nitrogenous heteroaromatic of ring B or singly-bound, and when the situation for concatenating group in its coupling chain containing ethenylidene, ethynylene, arlydene or inferior heteroaryl; X 1with ring A, X 2with ring B, X 3also can bond and form contracting ring with ring C; M1 and m3 separately represents the integer of 0 ~ 4, and m2 represents the integer of 1 ~ 3; At X 2during situation for singly-bound, m1 or m3 represents the integer of 1 ~ 4, and X 1or X 3represent concatenating group;
R 1~ R 3separately represent the substituting group without Anc1 ~ Anc3; N1 and n2 separately represents the integer of 0 ~ 3, and n3 represents the integer of 0 ~ 4; At R 1~ R 3each when there is multiple situations respectively, they also can mutually bond and form ring].
(25) according to the metal complex dye described in (24), wherein X 2be separately any one or group that they are combined of singly-bound or following formula (X-1) ~ formula (X-6),
[changing 11]
[in formula, Q 1represent and be selected from-S-,-O-,-N (R xA)-,-C (R xB) (R xC)-and-Si (R xB) (R xC)-in group; Herein, R xA~ R xCseparately represent hydrogen atom or substituting group; In addition, R xBwith R xCalso can bond and form ring mutually; R x1~ R x9separately represent hydrogen atom or substituting group; Herein, R x1with R x2, R x3with R x4, R x4with R x5, R x5with R xA, R x5with R xB, R x6with R x7, R x8with R x9respectively also can bond and form ring mutually; R x1~ R x4, R x6~ R x9also contracting ring can be formed with ring B bond; * represent the binding site with ring B, * * represents the binding site with Anc2].
(26) according to (24) or the metal complex dye described in (25), the wherein LD bidentate ligand that is following formula (2L-1) ~ formula (2L-5) represented by any one;
[changing 12]
[in formula, ring D, " represent aromatic ring; A 111~ A 141separately represent nitrogen-atoms anion or carbon atom anion, A 151represent nitrogen-atoms anion, oxygen atom anion or sulphur atom anion; R 111~ R 154separately represent hydrogen atom or not there is the substituting group of Anc1, Anc2 and Anc3; Herein, * represents the binding site with metal ions M].
(27) according to (24) or the metal complex dye described in (25), the wherein LD tridentate ligand that is following formula (3L-1) ~ formula (3L-4) represented by any one,
[changing 13]
[in formula, ring D, " represent aromatic ring; A 211~ A 242separately represent nitrogen-atoms or carbon atom; Wherein, each A 211with A 212, A 221with A 222, A 231with A 232, A 241with A 242at least one be anion; R 211~ R 241separately represent hydrogen atom or not there is the substituting group of Anc1, Anc2 and Anc3; Herein, * represents the binding site with metal ions M].
(28) described any one of (24) to (27) metal complex dye, wherein the bidentate ligand of above-mentioned LD or the atom being coordinated in metal ions M of tridentate ligand are nitrogen anion or carboanion, and there is following formula (SA) in part-structure
[changing 14]
[in formula, R dA1represent aryl, R dA2represent alkyl or aryl; R dA1with R dA2also can bond and form ring mutually; LL represents vinyl, acetenyl, arlydene or inferior heteroaryl; A represents the integer of 0 ~ 5].
(29) described any one of (24) to (28) metal complex dye, wherein X 2represented by following formula (X-1A) or formula (X-2A),
[changing 15]
[in formula, Rz represents that the σ p value of Hammett's rule is the substituting group of more than 0.05; Ring X represents aromatic carbon ring base or aromatic heterocycle; Herein, the associative key on the left of paper is binding on ring B, and Anc2 is binding on the associative key on the right side of paper].
(30) pigment solution, it is dissolved by metal complex dye described any one of above-mentioned (24) to (29) to form.
(31) according to the pigment solution described in (30), it makes the above-mentioned metal complex dye containing 0.001 quality % ~ 0.1 quality % in organic solvent and is suppressed to form at below 0.1 quality % by water.
(32) a kind of pigment adsorption electrode of dye-sensitized solar cell, it is after giving the pigment solution in the conductive support body having semiconductor microactuator particle described in coating basis (30) or (31), carries out reaction sclerosis and makes photoreceptor layers.
(33) manufacture method for dye-sensitized solar cell, it uses the pigment adsorption electrode of the dye-sensitized solar cell become described in above-mentioned (32), electrolyte and each material to electrode to assemble.
(34) compound, it is represented by following formula (AL),
[changing 16]
[in formula, ring A, ring B and ring C separately represent nitrogenous heteroaromatic; Herein, Z 1and the key between atom N and Z 2and the key between atom N can be singly-bound and also can be double bond; Z 1and Z 2separately represent carbon atom or nitrogen-atoms;
Anc1 ~ Anc3 separately represents acidic groups; L1 and l3 separately represents the integer of 1 ~ 4, and l2 represents the integer of 1 ~ 5;
X 1and X 3separately represent singly-bound or concatenating group, X 2for with the X of at least one Anc2 institute bond of pi-conjugated link 2atom and the concatenating group of nitrogenous heteroaromatic of ring B or singly-bound, and when the situation for concatenating group in its coupling chain containing ethenylidene, ethynylene, arlydene or inferior heteroaryl; X 1with ring A, X 2with ring B, X 3also can bond and form contracting ring with ring C; M1 and m3 separately represents the integer of 0 ~ 4, and m2 represents the integer of 1 ~ 3; At X 2during situation for singly-bound, m1 or m3 represents the integer of 1 ~ 4, and X 1or X 3represent concatenating group;
R 1~ R 3separately represent the substituting group without Anc1 ~ Anc3; N1 and n2 separately represents the integer of 0 ~ 3, and n3 represents the integer of 0 ~ 4; At R 1~ R 3each when there is multiple situations respectively, they also can mutually bond and form ring].
(35) according to the compound described in (34), wherein X 2for singly-bound, m1 or m3 is the integer of 1 ~ 4, and X 1or X 3for concatenating group.
In this manual, as long as no special instructions, then about carbon-to-carbon double bond, can be its any one when the situation of molecular memory at E type and Z-type, also can be their mixture in addition.When the substituting group represented with specific symbol or concatenating group, part etc. (hereinafter referred to as substituting group etc.) exist multiple, or simultaneously or when alternatively specifying multiple substituting groups etc., as long as no special instructions, then each substituting group etc. can mutually the same also can be different.This situation is also identical for the regulation of the number of substituting group etc.In addition, multiple substituting groups etc. close to time (time especially adjacent), as long as no special instructions, then they also can be interconnected and form ring.In addition, ring such as alicyclic ring, aromatic ring, heterocycle also can contracting ring and form condensed ring further.
In the present invention, each substituting group as long as no special instructions, then also can be substituted base further and replaced.
The effect of invention
According to the present invention, can provide a kind of the light absorption of long wavelength range is increased, the spectral sensitivity characteristic in this long wavelength range is improved thus photoelectric conversion efficiency is improved and to the absorption stability of semiconductive particles sub-surface or the photo-electric conversion element of excellent in te pins of durability and dye-sensitized solar cell.In addition, a kind of manufacture method of the metal complex dye, pigment solution, pigment adsorption electrode and the dye-sensitized solar cell that are suitable for above-mentioned photo-electric conversion element and dye-sensitized solar cell can be provided.
Above-mentioned and other feature of the present invention and advantage will be suitably more cheer and bright according to following record with reference to accompanying drawing.
Accompanying drawing explanation
The enlarged drawing of the circular portion in layer is also included to schematically show the profile that one of photo-electric conversion element of the present invention implements aspect by Fig. 1.
Fig. 2 is the profile of the dye-sensitized solar cell of the 2nd aspect schematically showing photo-electric conversion element of the present invention.
Fig. 3 is the visible absorption spectra figure of illustration metal complex dye D-25 in dimethyl formamide (Dimethylformamide, DMF) solution synthesized in embodiments of the invention.
Fig. 4 is the visible absorption spectra figure of illustration metal complex dye D-25 in the methanol solution of 340mmol/L tetrabutylammonium synthesized in embodiments of the invention.
Fig. 5 is the visible absorption spectra figure of illustration metal complex dye D-26 in the methanol solution of 340mmol/L tetrabutylammonium synthesized in embodiments of the invention.
Fig. 6 is the visible absorption spectra figure that the illustration metal complex dye D-26 making to synthesize in embodiments of the invention is adsorbed in the oxidation titanium film of gained on titanium oxide.
Fig. 7 is the visible absorption spectra figure of illustration metal complex dye D-28 in DMF solution synthesized in embodiments of the invention.
Fig. 8 is the visible absorption spectra figure that the illustration metal complex dye D-28 making to synthesize in embodiments of the invention is adsorbed in the oxidation titanium film of gained on titanium oxide.
Fig. 9 is the visible absorption spectra figure of illustration metal complex dye D-45 in the methanol solution of 340mmol/L tetrabutylammonium synthesized in embodiments of the invention.
Figure 10 is the visible absorption spectra figure of illustration metal complex dye D-59 in the methanol solution of 340mmol/L tetrabutylammonium synthesized in embodiments of the invention.
Figure 11 is the visible absorption spectra figure of illustration metal complex dye D-62 in DMF solution synthesized in embodiments of the invention.
Figure 12 is the visible absorption spectra figure that the illustration metal complex dye D-62 making to synthesize in embodiments of the invention is adsorbed in the oxidation titanium film of gained on titanium oxide.
Figure 13 is the visible absorption spectra figure of illustration metal complex dye D-97 in DMF solution synthesized in embodiments of the invention.
Figure 14 is the visible absorption spectra figure that the illustration metal complex dye D-97 making to synthesize in embodiments of the invention is adsorbed in the oxidation titanium film of gained on titanium oxide.
Figure 15 is the visible absorption spectra figure of illustration metal complex dye D-101 in DMF solution synthesized in embodiments of the invention.
Figure 16 is the visible absorption spectra figure that the illustration metal complex dye D-101 making to synthesize in embodiments of the invention is adsorbed in the oxidation titanium film of gained on titanium oxide.
Figure 17 is the visible absorption spectra figure of illustration metal complex dye D-136 in DMF solution synthesized in embodiments of the invention.
Figure 18 is the visible absorption spectra figure that the illustration metal complex dye D-136 making to synthesize in embodiments of the invention is adsorbed in the oxidation titanium film of gained on titanium oxide.
Figure 19 is the visible absorption spectra figure of illustration metal complex dye D-140 in DMF solution synthesized in embodiments of the invention.
Figure 20 is the visible absorption spectra figure that the illustration metal complex dye D-140 making to synthesize in embodiments of the invention is adsorbed in the oxidation titanium film of gained on titanium oxide.
Figure 21 is the visible absorption spectra figure of illustration metal complex dye D-141 in DMF solution synthesized in embodiments of the invention.
Figure 22 is the visible absorption spectra figure that the illustration metal complex dye D-141 making to synthesize in embodiments of the invention is adsorbed in the oxidation titanium film of gained on titanium oxide.
Figure 23 is the visible absorption spectra figure of illustration metal complex dye D-187 in DMF solution synthesized in embodiments of the invention.
Figure 24 is the visible absorption spectra figure that the illustration metal complex dye D-187 making to synthesize in embodiments of the invention is adsorbed in the oxidation titanium film of gained on titanium oxide.
Figure 25 is the visible absorption spectra figure of illustration metal complex dye D-188 in DMF solution synthesized in embodiments of the invention.
Figure 26 is the visible absorption spectra figure that the illustration metal complex dye D-188 making to synthesize in embodiments of the invention is adsorbed in the oxidation titanium film of gained on titanium oxide.
Figure 27 is the visible absorption spectra figure that the illustration metal complex dye D-57 making to synthesize in embodiments of the invention is adsorbed in the oxidation titanium film of gained on titanium oxide.
Figure 28 is the visible absorption spectra figure that the illustration metal complex dye D-280 making to synthesize in embodiments of the invention is adsorbed in the oxidation titanium film of gained on titanium oxide.
Figure 29 is the compound 13 synthesized in embodiments of the invention 1h-NMR spectrogram.
Figure 30 is the compound 26 synthesized in embodiments of the invention 1h-NMR spectrogram.
Figure 31 is the compound 27 synthesized in embodiments of the invention 1h-NMR spectrogram.
Figure 32 is the compound 34 synthesized in embodiments of the invention 1h-NMR spectrogram.
Embodiment
<< photo-electric conversion element and dye-sensitized solar cell >>
Photo-electric conversion element of the present invention such as shown in Figure 1, photo-electric conversion element 10 comprise conductive support body 1, containing utilize pigment (metal complex dye) 21 sensitizing semiconductor microactuator particle photoreceptor layers 2, as the Charger transfer body layer 3 of hole transmission layer and to electrode 4.Herein, in the present invention, preferably on semiconductor microactuator particle 22, be adsorbed with pigment (metal complex dye) 21 and be adsorbed with coadsorbent.The conductive support body 1 being provided with photoreceptor layers 2 plays function as active electrode in photo-electric conversion element 10.In this example, system 100 is shown, this system 100 is the mode this photo-electric conversion element 10 can be used in the battery use utilizing external circuit 6 to make actuating mechanism M work to utilize dye-sensitized solar cell.
In this example, comprise conductive support body 1 and photoreceptor layers 2 by optoelectronic pole 5, this photoreceptor layers 2 is containing the semiconductor microactuator particle being adsorbed with pigment (metal complex dye) 21.Photoreceptor layers 2 can design according to object, can be individual layer formation and also can be multilayer formation.Pigment (metal complex dye) 21 in one deck photoreceptor layers can be and a kind ofly also can be multiple mixing, and wherein at least one uses the metal complex dye of the invention described above.Pigment (metal complex dye) 21 excites by the light be incident in photoreceptor layers 2.Pigment through exciting has the high electronics of energy, and this electronics migrates on the conduction band (conduction band) of semiconductor microactuator particle 22 from pigment (metal complex dye) 21, and then arrives conductive support body 1 by spreading.Now, pigment (metal complex dye) 21 becomes oxysome, but the electronics on electrode utilizes external circuit 6 and works, simultaneously via getting back in the oxysome and electrolytical photoreceptor layers 2 that there is pigment (metal complex dye) 21 to electrode 4, play a role as solar cell thus.
About the manufacture method for the material in photo-electric conversion element or dye-sensitized solar cell and each component in the present invention, unless otherwise specified, as long as what then adopt in the manufacture method of this kind of material and each component is common, such as can refer to United States Patent (USP) the 4th, 927, No. 721 specifications, United States Patent (USP) the 4th, 684, No. 537 specifications, United States Patent (USP) the 5th, 084, No. 365 specifications, United States Patent (USP) the 5th, 350, No. 644 specifications, United States Patent (USP) the 5th, 463, No. 057 specification, United States Patent (USP) the 5th, 525, No. 440 specifications, Japanese Patent Laid-Open 7-249790 publication, Japanese Patent Laid-Open 2004-220974 publication, Japanese Patent Laid-Open 2008-135197 publication.
Below, the outline of main member of the present invention is illustrated.
< photoreceptor layers >
Photoreceptor layers is the layer containing aftermentioned electrolyte and containing semiconductor microactuator particle, and above-mentioned semiconductor microactuator particle carries the sensitizing coloring matter containing following metal complex dye of the present invention.
<< metal complex dye >>
Metal complex dye of the present invention is represented by following general formula (I).
M (LA) (LD) (LX) mX(CI) mYformula (I)
In formula (I), M represents metal ion.
LA represents the tridentate ligand represented by following formula (AL).
LD represents bidentate ligand or the tridentate ligand different from this LA.Herein, in this bidentate ligand or this tridentate ligand is anion with at least one of the coordination atom of metal ions M bond.What is called is anion, represent hydrogen atom dissociate and with M bond.
LX represents monodentate ligand.MX represents 1 when LD is bidentate ligand, represents 0 when LD is tridentate ligand.
CI represent must gegenion to make the gegenion during situation of charging neutrality.
MY represents the integer of 0 ~ 3.
[changing 17]
In formula (AL), ring A, ring B and ring C separately represent nitrogenous heteroaromatic.Herein, Z 1and the key between atom N and Z 2and the key between atom N can be singly-bound and also can be double bond.Z 1and Z 2separately represent carbon atom or nitrogen-atoms.
Anc1 ~ Anc3 separately represents acidic groups.L1 and l3 separately represents the integer of 1 ~ 4, and l2 represents the integer of 1 ~ 5.
X 1and X 3separately represent singly-bound or concatenating group, X 2for with the X of at least one Anc2 institute bond of pi-conjugated link 2atom and the concatenating group of nitrogenous heteroaromatic of ring B or singly-bound, and when the situation for concatenating group in its coupling chain containing ethenylidene, ethynylene, arlydene or inferior heteroaryl.X 1with ring A, X 2with ring B, X 3also can bond and form contracting ring with ring C.M1 and m3 separately represents the integer of 0 ~ 4, and m2 represents the integer of 1 ~ 3.At X 2during situation for singly-bound, m1 or m3 represents the integer of 1 ~ 4, and X 1or X 3represent concatenating group.
R 1~ R 3separately represent the substituting group without Anc1 ~ Anc3.N1 and n2 separately represents the integer of 0 ~ 3, and n3 represents the integer of 0 ~ 4.At R 1~ R 3each when there is multiple situations respectively, they also can bond and form ring mutually.Ring A and ring B, ring B and ring C also can via concatenating group bond.
-metal ions M-
M is the central metal of metal complex dye, can enumerate the element of long period Biao Shang 6 race ~ 12 race.
This kind of element can be enumerated: ruthenium (Ru), iron (Fe), osmium (Os), copper (Cu), tungsten (W), chromium (Cr), molybdenum (Mo), nickel (Ni), palladium (Pd), platinum (Pt), cobalt (Co), iridium (Ir), rhodium (Rh), rhenium (Re), manganese (Mn) and zinc (Zn).
In the present invention, metal ions M is preferably Os 2+, Ru 2+or Fe 2+, be more preferably Os 2+, Ru 2+, be wherein especially preferably Ru 2+.
Moreover be set under the state in photo-electric conversion element, the valence mumber of above-mentioned M changes because of the redox reaction with adjacent material sometimes.
-ligand L A-
In the present invention, the tridentate ligand of ligand L A represented by above-mentioned formula (AL) or compound.
Ligand L A is the part with the absorption base being adsorbed in semiconductor microactuator particle surface.
Below, the tridentate ligand represented by formula of the present invention (AL) or compound are described in detail.
As long as the heteroaromatic of ring A ~ ring C has nitrogen-atoms and is aromatic rings in one-tenth ring hetero atom, then can be arbitrary ring.
The heteroaromatic of ring A ~ ring C is preferably 5 rings or 6 rings, and these heteroaromatics also can carry out contracting ring with aromatic carbon ring, heteroaromatic, not aromatic heterocycle, alicyclic ring.In addition, the one-tenth ring hetero atom of heteroaromatic can be 2 ~ 6 nitrogen-atoms, also can also such as, containing other hetero-atoms, oxygen atom, sulphur atom except nitrogen-atoms.
In the present invention, heteroaromatic is preferably 6 rings of non-contracting ring, 6 rings through 5 ring contracting rings, 5 rings through phenyl ring contracting ring or 6 rings through phenyl ring contracting ring, be more preferably 6 rings of non-contracting ring, 6 rings through 5 ring contracting rings, and then be preferably 6 rings of non-contracting ring.
As heteroaromatic, such as 6 rings can enumerate pyridine ring, pyrimidine ring, pyrazine ring, triazine ring, quinoline ring, quinazoline ring, and 5 rings can enumerate pyrrole ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, benzimidazole ring, benzoxazole ring, benzothiazole ring, indole ring, indazole ring.
Ring B is preferably 6 rings of non-condensation, is more preferably pyridine ring, pyrazine ring, pyrimidine ring, triazole ring, and then is preferably pyridine ring, pyrimidine ring, is especially preferably pyridine ring.
Ring A and ring C be preferably non-condensation 6 rings, through 6 rings of 5 ring contracting rings, 6 rings through phenyl ring contracting ring.6 rings are more preferably the ring be separately selected from pyridine ring, pyrimidine ring, triazine ring, imidazole ring, benzimidazole Huan, oxazole ring, thiazole ring, benzothiazole Huan, oxadiazole rings, Thiadiazole, isoxazole ring, isothiazole ring, triazole ring and pyrazole ring, wherein so be preferably pyridine ring, pyrimidine ring, be especially preferably pyridine ring.6 rings through 5 ring contracting rings are preferably the pyridine ring through furan nucleus contracting ring, the pyridine ring through thiphene ring contracting ring, through the pyridine ring of pyrrole ring contracting ring, cough up the pyridine ring of ring (silole ring) contracting ring, the pyridine ring through cyclopentadienyl rings contracting ring through thiophene, be more preferably through the pyridine ring of furan nucleus contracting ring, the pyridine ring through thiphene ring contracting ring, and then be preferably the pyridine ring through thiphene ring contracting ring.
With regard to the viewpoint of long wavelengthization, Z 1and Z 2being preferably at least one is carbon atom, is more preferably two situations for carbon atom.
Anc1 ~ Anc3 is the absorption base being adsorbed in semiconductor microactuator particle surface, at least utilizes in them absorption base and adsorbs this semiconductor microactuator particle surface.
Anc1 ~ Anc3 represents the acidic groups as adsorptivity base.
In the present invention, in the part represented by formula (AL), preferably there are at least 2 acidic groups, be more preferably and there are 3 acidic groups.
(acidic groups)
Herein, so-called acidic groups, refers to the substituting group of the proton with dissociative, and pKa is less than 11.Include, for example: carboxyl, phosphono (phosphonyl), phosphoryl (phosphoryl), sulfo group, boronate etc. demonstrate acid group and acidic group; or the group of any one had in them; with regard to the viewpoint of electron injection, be preferably carboxyl or there is the group of this carboxyl.In addition, the form that acidic groups also can be taked to discharge proton and dissociate, also can be salt.
When acidic groups is the situation of salt, gegenion when forming this salt is not particularly limited, and include, for example the example of the cation shown in gegenion CI in aftermentioned formula (I).
In the present invention, with regard to the viewpoint of electro transfer, be especially preferably carboxyl.
In addition, a preferred aspect of acidic groups can enumerate following formula (Anc).
[changing 18]
In formula, Zx represents singly-bound or-[C (=W 3)] nx-.Herein, nx represents the integer of 1 ~ 3.=W 1,=W 2and=W 3separately expression=O or=C (Ra1) (Ra2).Ra1 and Ra2 separately represents substituting group.Moreover-the OH in above-mentioned formula also can form salt.
In formula (Anc), W 1~ W 3=C (Ra1) (Ra2) in the substituting group of Ra1 and Ra2 can enumerate aftermentioned substituting group T.Ra1 and Ra2 is more preferably alkyl, aryl, heterocyclic radical, cyano group, acyl group, sulfonyl, alkoxy carbonyl, aryloxycarbonyl, carbamyl, sulfamic, and then is preferably alkyl, aryl, cyano group.
Group represented by formula (Anc) be preferably following formula (Anc-1) ~ formula (Anc-5) any one represented by group.
[changing 19]
In formula, Ra1 ~ Ra4 separately represents substituting group.-OH in above-mentioned formula also can form salt.
The substituting group of Ra1 ~ Ra4 and above-mentioned Ra1 and Ra2 are synonymous, and preferable range is also identical.
In group represented by formula (Anc-1) ~ formula (Anc-5), be preferably formula (Anc-1), group represented by formula (Anc-5), be especially preferably the group represented by formula (Anc-1)
X in formula (AL) 1~ X 3represent singly-bound or concatenating group.Wherein, X 2for with the X of at least one Anc2 institute bond of pi-conjugated link 2atom and the concatenating group of nitrogenous heteroaromatic of ring B or singly-bound, and when the situation for concatenating group in its coupling chain containing ethenylidene or ethynylene.During situation containing ethenylidene, the substituting group on ethenylidene also can link with adjacent group and form ring.The situation forming ring also comprises the situation forming aromatic rings.X 1with ring A, X 2with ring B, X 3also can bond and form contracting ring with ring C.At X 2during situation for singly-bound, m1 or m3 represents the integer of 1 ~ 4, and X 1or X 3represent concatenating group.
X 2as long as meet above-mentioned condition, be then not particularly limited.Concatenating group comprises the ethenylidene, ethynylene, arlydene, the inferior heteroaryl that are substituted or are unsubstituted, and comprises the group of these moiety combinations.Inferior heteroaryl is that above-mentioned ethenylidene is at X 2interior link and form ring gained, this kind is at X 2interior link and the heteroaromatic formed in the inferior heteroaryl of ring can enumerate furan nucleus, thiphene ring, pyrrole ring, cyclopentadiene ring, thiophene cough up ring.Arlydene is that above-mentioned ethenylidene is at X 2interior link and form ring gained, this kind is at X 2interior link and the aryl rings formed in the arlydene of ring can enumerate phenyl ring, naphthalene nucleus, is preferably phenyl ring.
Heteroaromatic in inferior heteroaryl is preferably furan nucleus, thiphene ring, is more preferably thiphene ring.
As the group that ethenylidene, ethynylene, arlydene, inferior heteroaryl are combined, such as also as the alkynylene of the alkenylene of more than 2 (being preferably 2 or 3), more than 2 (being preferably 2 or 3), identical group can be combined continuously, in addition also can by different moiety combinations.When this situation, can enumerate :-ethenylidene-ethynylene-,-ethynylene-ethenylidene-,-ethenylidene-inferior heteroaryl-,-ethynylene-inferior heteroaryl-,-inferior heteroaryl-ethenylidene-,-inferior heteroaryl-ethynylene-,-arylene-vinylenes-,-inferior heteroaryl-ethynylene-,-inferior heteroaryl-inferior heteroaryl-etc.Include, for example :-divalence thiphene ring-ethynylene-,-divalence thiphene ring-ethenylidene-,-ethenylidene-divalence thiphene ring-,-ethynylene-divalence thiphene ring-,-divalence furan nucleus-ethynylene-,-divalence phenyl ring-ethynylene-,-divalence thiphene ring-divalence thiphene ring-,-divalence furan nucleus-divalence furan nucleus-,-ethynylene-ethynylene-.
X 2be preferably is separately any one or the group that they combined of singly-bound or following formula (X-1) ~ formula (X-6).
[changing 20]
In formula, Q 1represent and be selected from-S-,-O-,-N (R xA)-,-C (R xB) (R xC)-and-Si (R xB) (R xC)-in group.Herein, R xA~ R xCseparately represent hydrogen atom or substituting group.In addition, R xBwith R xCalso can bond and form ring mutually.R x1~ R x9separately represent hydrogen atom or substituting group.Herein, R x1with R x2, R x3with R x4, R x4with R x5, R x5with R xA, R x5with R xB, R x6with R x7, R x8with R x9respectively also can bond and form ring mutually.R x1~ R x4, R x6~ R x9also contracting ring can be formed with ring B bond.* represent the binding site with above-mentioned ring B, * * represents the binding site with above-mentioned Anc2.
With regard to the viewpoint of long wavelengthization, X 2be separately preferably formula (X-1), formula (X-5) any one.With regard to improving the viewpoint of molar absorption coefficient, be preferably singly-bound or formula (X-6).In addition, with regard to improving the viewpoint of the quantum yield of photo-electric conversion element, singly-bound is preferably.
Preferred aspects has following aspect A and aspect B, and more preferably aspect is aspect A.
Aspect A
X 2represent any one or the group that they combined of singly-bound, above-mentioned formula (X-1) ~ formula (X-6), be more preferably singly-bound, formula (X-1), formula (X-5) any one.Wherein, the R in formula (X-1) x1and R x2be hydrogen atom, R x1for hydrogen atom and R x2for alkyl or aryl, or R x1for alkyl or aryl and R x2for hydrogen atom.Alkyl, aryl also can have substituting group, and substituting group can enumerate aftermentioned substituting group T.Be more preferably R x1and R x2be hydrogen atom, or R x1for hydrogen atom and R x2for alkyl.Absorption efficiency, photoelectric conversion efficiency, durability can be improved thus.
Aspect B
X 2there is the structure of=C (Rz)-represented in pi-conjugated part-structure.Herein, "=" associative key is positioned at above-mentioned ring B side, and "-" associative key is positioned at above-mentioned Anc2 side.
The σ p value of the expression Hammett's rule of above-mentioned Rz is the substituting group of more than 0.05.Especially can improve the absorption efficiency of the long wavelength range of more than 900nm thus, or improve absorption stability.
The σ p value of Hammett's rule be more than 0.05 substituting group include, for example: cyano group, acyl group, aryl carbonyl, Heteroarylcarbonyl, sulfonyl, alkoxy carbonyl, aryloxycarbonyl, carbamyl, sulfamic, perfluoroalkyl, halogen atom, nitro, heteroaryl or there is the aryl etc. of these groups.
Rz is preferably cyano group, acyl group (being preferably acetyl group), aryl carbonyl, perfluoroalkyl (being preferably trifluoromethyl), halogen atom, heteroaryl or has the aryl of these groups, is especially preferably acyl group (being preferably acetyl group), aryl carbonyl, halogen atom (being preferably fluorine atom), heteroaryl (being preferably pyridine radicals, pyrimidine radicals).
Wherein, Rz is preferably-C (=O) R z1, perfluoroalkyl, halogen atom, heteroaryl or cyano group.Herein, R z1represent alkyl, aryl, heterocyclic radical.
This kind of X 2preferred aspects can enumerate following formula (X-1A) or the group represented by formula (X-2A).
[changing 21]
In formula, Rz represents that the σ p value of Hammett's rule is the substituting group of more than 0.05.Ring X represents aromatic carbon ring base or aromatic heterocycle.Herein, the associative key on the left of paper is binding on the associative key of above-mentioned ring B, Anc2 bond on the right side of paper.
The preferable range of Rz is described above.
Above-mentioned formula (X-1A) or the group represented by formula (X-2A) and then be preferably following formula (X-1B), group represented by formula (X-2B), be especially preferably formula (X-1B).
[changing 22]
In formula, the associative key on the left of paper and ring B bond.Rz in Rz in formula (X-1B), formula (X-2B) and above-mentioned formula (X-1A), formula (X-2A) is synonymous, and preferable range is also identical.
Explanation common in aspect A, aspect B is below shown.
X in formula (AL) 1and X 3represent singly-bound or concatenating group.
X 1and X 3concatenating group also can contain in coupling chain-O-,-S-,-NR ' (R represents hydrogen atom or substituting group)-, more than divalence representative examples of saturated aliphatic base, have do not form more than the divalence of the unsaturated group of conjugation with this ring A, ring C unsaturated aliphatic base, the hydrocarbon cyclic base of more than divalence non-aromatic, more than divalence non-aromatic heterocyclic radical.
X 1and X 3concatenating group also can be pi-conjugated conjugated chain, when this situation, above-mentioned X can be enumerated 2in the concatenating group enumerated.
X 1and X 3be preferably singly-bound or above-mentioned pi-conjugated conjugated chain.
X 1and X 3be preferably the situation of any one that any one is formula (X-1) ~ formula (X-6), be more preferably the situation of any one that two are formula (X-1) ~ formula (X-6).X 1and X 3and then be preferably the situation that any one is formula (X-1) or formula (X-6), and then be more preferably the situation that two are formula (X-1) or formula (X-6).
11 ~ 13 are preferably 1 or 2, are more preferably 1.
M1 and m3 represents the integer of 0 ~ 4, is preferably 0 or 1, with regard to the viewpoint of photoelectric conversion efficiency, absorption stability, be preferably of m1 and m3 be 0 and another be 1 situation or two be the situation of 1, be more preferably the situation that two is 1.
M2 is preferably 1 or 2, is more preferably 1.
R in formula (AL) 1~ R 3represent substituting group, this substituting group can enumerate aftermentioned substituting group T.R 1~ R 3the σ p value being preferably the Hammett such as alkyl, aryl, heterocyclic radical, amino, alkoxyl, aryloxy group, alkylthio group, arylthio and halogen atom, cyano group, sulfonyl is positive electron-withdrawing base, is more preferably alkyl, alkyl-carbonyl, aryl carbonyl, aryl, heterocyclic radical, amino, halogen atom (being preferably fluorine atom), cyano group.
N1 and n3 be preferably 0 or 1, n2 be preferably 0.
Part represented by above-mentioned formula (AL) is preferably the part represented by following formula (AL-1).
[changing 23]
In formula, Anc1 ~ Anc3, X 1~ X 3, R 1~ R 3, 11 ~ 13, Anc1 ~ Anc3, X in m1 ~ m3, n1 ~ n3 and above-mentioned formula (AL) 1~ X 3, R 1~ R 3, 11 ~ 13, m1 ~ m3, n1 ~ n3 be synonymous, preferable range is also identical.
Moreover with regard to the viewpoint as compound, the part represented by formula (AL) is preferably X 2for singly-bound, m1 or m3 be 1 ~ 4 integer and X 1or X 3for the compound of concatenating group, or X 2for the R in formula (X-1) or formula (X-5), formula (X-1) x1for hydrogen atom and R x2for alkyl or aryl, m1 or m3 be 1 ~ 4 integer and X 1or X 3for the compound of concatenating group, be more preferably X 2for singly-bound, m1 or m3 be 1 ~ 4 integer and X 1or X 3for the compound of concatenating group, and then be preferably X 2for singly-bound, m1 or m3 be 1 ~ 4 integer and X 1or X 3for the compound of formula (X-1) or formula (X-5).
Below, the preferred structure as compound can be represented by following formula (AC-1) or formula (AC-2).
[changing 24]
In formula, R y1and R y2represent hydrogen atom or substituting group.
R y1and R y2substituting group can enumerate aftermentioned substituting group T.
Herein, R y1at least one represent alkyl or aryl, be preferably at least one be alkyl, being more preferably is all alkyl.
R y2be preferably hydrogen atom or link with pyridine ring and form the group of ring J as the formula (AC-2 ') of following structure.Ring J represents and can contain heteroatomic aromatic rings, is preferably thiphene ring.
[changing 25]
Below, the concrete example of the part (compound) represented by formula of the present invention (AL) is shown, but the present invention is not limited to these concrete examples.
[changing 26]
[changing 27]
[changing 28]
[changing 29]
[changing 30]
[changing 31]
[changing 32]
[changing 33]
[changing 34]
[changing 35]
[changing 36]
[changing 37]
[changing 38]
These parts can utilize following methods to synthesize: Japanese Patent Laid-Open 2012-508227 publication, Japanese Patent Laid-Open 2011-502965 publication, Japanese Patent Laid-Open 2011-502187 publication, " the international version (Angew.Chem.Int.Ed.) of German applied chemistry " (2011 years, 50th volume, 1-6 page) middle method, the method recorded in the list of references enumerated in the document or the method according to these methods recorded.
Moreover, the synthetic method of preferred part (compound) of the present invention is also not particularly limited, with regard to manufacturing the viewpoint of adaptive or synthesis easiness, preferably use any one of the compound represented by following formula (AD-1) ~ formula (AD-3).
[changing 39]
In formula, R y1and R y2with the R in above-mentioned formula (AC-1), formula (AC-2) y1and R y2for synonymous, preferable range is also identical.R y4and R y5represent hydrogen atom or alkyl.R y6represent-COOH ,-COOR y7,-CHO (aldehyde) any one.Herein, R y7represent alkyl.
R y3represent-COOH ,-COOR y7,-CHO (aldehyde), following structure (also can be substituted further) any one, wherein, R y3at least one represent-CHO (aldehyde) or following structure.
[changing 40]
In formula, 2 R gseparately represent alkyl, also can bond and form ring mutually.Herein, * represents binding site.
Compound represented by general formula (AC-1), general formula (AC-2), general formula (AD-1) ~ general formula (AD-3) specifically can enumerate following compound.
Herein, Et is ethyl (-C 2h 5).
[changing 41]
-ligand L D-
In the present invention, ligand L D is divided in alms giver's part one class, does not preferably have the part of the absorption base being adsorbed in semiconductor microactuator particle surface.
Moreover, even if containing being equivalent to the group adsorbing base in part, also containing to be binding on the form of the group of metal ions M, not being adsorbed in semiconductor microactuator particle surface.
Moreover the absorption base being adsorbed in semiconductor microactuator particle surface is the substituent A nc1 ~ substituent A nc3 in above-mentioned ligand L A.
Ligand L D represents bidentate ligand or the tridentate ligand different from this LA.Herein, in the bidentate ligand of ligand L D or tridentate ligand is anion with at least one of the coordination atom of metal ions M bond.What is called is anion, represent hydrogen atom dissociate and with M bond.
Ligand L D is preferably the part represented by following formula (DL).
[changing 42]
In formula, ring D ', ring E ' and ring F separately represent the aromatic rings of 5 rings or 6 rings, R a, R a1and R a4separately represent substituting group.Mb represents 0 or 1.Ma1 and ma4 separately represents the integer of 0 ~ 3.Ma represents the integer of 0 ~ 4 when mb is 0, represent the integer of 0 ~ 3 when mb is 1.
Herein, when ma, ma1 and ma4 are respectively the integer of more than 2, multiple R a, multiple R a1and multiple R a4also can bond and form ring mutually.
5 rings of ring D ', ring E ' and ring F or the aromatic rings of 6 rings contain aromatic carbon ring or heteroaromatic.In addition, the aromatic rings of 5 rings or 6 rings also can through aromatic rings, heterocycle, alicyclic ring contracting ring.
Aromatic carbon ring can enumerate phenyl ring, naphthalene nucleus, and heteroaromatic can enumerate the heteroaromatic enumerated in the ring A ~ ring C in above-mentioned formula (AL), and these rings are preferred.
Ring F is preferably nitrogenous heteroaromatic, and is preferably the nitrogenous heteroaromatic enumerated in ring B, is more preferably pyridine ring and pyrimidine ring, triazine ring, and then is preferably pyridine ring and pyrimidine ring, with regard to the viewpoint of long wavelengthization, is especially preferably pyridine ring.
Herein, ring D ', ring E ' and ring F are preferably containing the coordination atom with metal ions M bond, and this coordination atom is preferably the anion of carbon atom, nitrogen-atoms, sulphur atom, oxygen atom or these atoms.Be preferably at least one of this coordination atom with ionic bond and metal ions M bond.
Can enumerate with the group of ionic bond and metal ions M bond :-CO 2 -ion ,-O -ion ,=C --ion (carbon ion of such as aromatic rings) ,-S -ion, > N -ion ,-N -sO 2-ion (if represent with monad radical, is then-N -sO 2r y, R yrepresent substituting group).
Wherein, the atom forming ring preferably can enumerate=C --ion, > N -carboanion, nitrogen anion that ion is such.
R a, R a1and R a4substituting group can enumerate aftermentioned substituting group T.R aaftermentioned R can be enumerated 111~ R 154in the substituting group enumerated, preferable range is also identical.R a1and R a4be preferably alkyl, thiazolinyl (being preferably vinyl), alkynyl (being preferably acetenyl), aryl, heterocyclic radical (being preferably aromatic heterocycle), halogen atom, alkoxyl, aryloxy group, alkylthio group, arylthio, amino, cyano group, alkyl sulphonyl, aryl sulfonyl; be more preferably halogenated alkyl, halogenated aryl, halogen atom, cyano group, alkyl sulphonyl, aryl sulfonyl; and then be preferably halogenated alkyl, halogen atom, cyano group, be especially preferably halogenated alkyl.
Ma, ma1 and ma4 are preferably the integer of 0 ~ 2, are more preferably 1 or 2.Mb is preferably 1.
Ligand L D is preferably following formula (DL-1) or the part represented by formula (DL-2).
[changing 43]
R a2and R a3separately represent substituting group, ma2 represents the integer of 0 ~ 3, and ma3 represents the integer of 0 ~ 4.R a1, R a4, R in ma1, ma4 and above-mentioned formula (DL) a1, R a4, ma1, ma4 be synonymous, preferable range is also identical.
R a2and R a3r in represented substituting group and above-mentioned formula (DL) afor synonymous, preferable range is also identical.
When ma1 ~ ma4 is respectively the integer of more than 2, multiple R a1~ multiple R a4also can bond and form ring mutually.
Ring D and ring E separately represents the aromatic rings of 5 rings or 6 rings.This aromatic rings can enumerate the ring enumerated in ring D ' in above-mentioned formula (DL) and ring E ', and preferred aromatic rings is also identical with the ring enumerated in ring D ' and ring E '.
Moreover, the D in ring D, ring E 1, D 2and the key between the carbon atom of pyridine ring institute bond can be singly-bound and also can be double bond.
D 1and D 2separately represent carbon atom anion or nitrogen-atoms anion.
Ring D and ring E is preferably pyrazole ring, triazole ring or phenyl ring.
In addition, when ligand L D is the situation of bidentate ligand, be preferably following formula (2L-1) ~ formula (2L-5) any one represented by bidentate ligand.
[changing 44]
In formula (2L-1) ~ formula (2L-5), * represents the binding site with metal ions M.Ring D " represents aromatic ring.A 111~ A 141separately represent nitrogen-atoms anion or carbon atom anion, A 151represent any one of nitrogen-atoms anion, oxygen atom anion or sulphur atom anion.R 111~ R 154separately represent hydrogen atom or not there is the substituting group of Anc1, Anc2 and Anc3.
Herein, A 111~ A 141for forming ring D " nitrogen-atoms or carbon atom on the hydrogen atom of bond depart from and the carbon atom anion that obtains or nitrogen-atoms anion.A 151especially the situation removing the residue of reactive hydrogen gained in the functional group in aromatic carbon ring and nitrogen-containing hetero aromatic rings in (being substituted) amino, hydroxyl or mercapto is preferably.In formula (2L-1) ~ formula (2L-5), ring D " can enumerate aromatic carbon ring, containing oxygen heteroaromatic, sulfur-containing aromatic heterocycle, nitrogenous heteroaromatic.Aromatic carbon ring can enumerate phenyl ring, naphthalene nucleus etc., and be preferably phenyl ring, be preferably furan nucleus containing oxygen heteroaromatic, sulfur-containing aromatic heterocycle is preferably thiphene ring.Nitrogenous heteroaromatic is preferably the nitrogenous heteroaromatic in the heteroaromatic enumerated in ring A ~ ring D, is more preferably pyrrole ring, pyrazole ring, imidazole ring, triazole ring.A in formula (2L-1) ~ formula (2L-4) 111~ A 141form the ring D before anion " and the middle A of formula (2L-5) 151the ring D replaced " such as can preferably enumerate: phenyl ring or thiphene ring, furan nucleus, or the anionicsite of following formula (a-1) ~ formula (a-5), formula (a-1a), formula (a-2a), formula (a-1b) and the group represented by formula (a-4a) replaces the ring etc. of gained through hydrogen atom.
[changing 45]
In formula, Rd represents substituting group.B1 represents the integer of 0 ~ 2, and b2 represents the integer of 0 ~ 3, and b3 represents 0 or 1.When b1 is 2 or when b2 is more than 2, multiple Rd each other also can bond and form ring mutually.Rd include, for example aftermentioned substituting group T.
[changing 46]
In formula, in Rd, b1 ~ b3 and above-mentioned formula (a-1) ~ formula (a-5) Rd, b1 ~ b3 is synonymous, preferable range is also identical.B4 represents each integer of 0 ~ 4, and b5 represents each integer of 0 ~ 5.Moreover in formula (a-1a), formula (a-1b), expression not only can have Rd on phenyl ring, also can have Rd on pyrrole ring.
Rd is preferably the alkyl of straight chain or branch, cycloalkyl, thiazolinyl, fluoroalkyl, aryl, halogen atom, alkoxy carbonyl, cyclo alkoxy carbonyl and the group by these moiety combinations, and then be preferably the alkyl of straight chain or branch, cycloalkyl, thiazolinyl, fluoroalkyl, aryl and the group by these moiety combinations, be especially preferably the alkyl of straight chain or branch, cycloalkyl, thiazolinyl, fluoroalkyl and the group by these moiety combinations.
R 111~ R 154represented substituting group include, for example aftermentioned substituting group T, is wherein preferably aromatic heterocycle, aromatic carbon ring base, vinyl, acetenyl, halogen atom, alkyl, amino (comprises alkyl amino, dialkyl amido, arylamino, ammonia diaryl base, N-alkyl-N-arylamino etc.), alkoxyl, aryloxy group, alkylthio group, arylthio, silylation, is more preferably aromatic heterocycle, aromatic carbon ring base, vinyl, alkyl, amino (comprises alkyl amino, dialkyl amido, arylamino, ammonia diaryl base etc.), and then be preferably aromatic heterocycle, there is alkyl or alkoxyl or amino and (comprise alkyl amino, dialkyl amido, arylamino, ammonia diaryl base etc.) aromatic carbon ring base, amino (comprises alkyl amino, dialkyl amido, arylamino, ammonia diaryl base etc.), especially preferably there is amino and (comprise alkyl amino, dialkyl amido, arylamino, ammonia diaryl base etc.) aromatic carbon ring base, amino (comprises alkyl amino, dialkyl amido, arylamino, ammonia diaryl base etc.).
When ligand L D is the situation of tridentate ligand, be preferably following formula (3L-1) ~ formula (3L-4) any one represented by tridentate ligand.
[changing 47]
In formula (3L-1) ~ formula (3L-4), * represents the binding site with metal ions M.Ring D " represents aromatic ring.A 211~ A 242separately represent nitrogen-atoms or carbon atom.Wherein, each A 211with A 212, A 221with A 222, A 231with A 232, A 241with A 242at least one be anion.R 211~ R 241separately represent hydrogen atom or not there is the substituting group of Anc1, Anc2 and Anc3.
A 211~ A 242in be anion with the A of above-mentioned formula (2L-1) ~ formula (2L-5) 111~ A 141for synonymous.A 211~ A 242in do not have anion for not having carbon atom or the nitrogen-atoms of hydrogen atom.Ring D " with the ring D of above-mentioned formula (2L-1) ~ formula (2L-5) " in formula (3L-1) ~ formula (3L-4) is synonymous, and specifically, ring D " can enumerate aromatic carbon ring, nitrogenous heteroaromatic.Aromatic carbon ring can enumerate phenyl ring, naphthalene nucleus, and nitrogenous heteroaromatic is preferably the nitrogenous heteroaromatic in the heteroaromatic enumerated in ring A ~ ring D.Ring D is more preferably containing A 111~ A 141the aromatic ring of any one and carbon atom or 2 carbon atoms.Now, 2 ring D in various " can identical also can be different.Substituent R 211~ substituent R 241with the substituent R of above-mentioned formula (2L-1) ~ formula (2L-5) 111~ substituent R 154for synonymous, preferably also identical.
Moreover in the present invention, in the bidentate ligand of above-mentioned LD or tridentate ligand, the atom being coordinated in metal ions M is nitrogen anion or carboanion and has the long wavelengthization especially realizing absorbing of arylamino or ammonia diaryl base in substituting group, therefore preferably.
Specifically, above-mentioned preferred part to be the atom being coordinated in metal ions M be nitrogen anion or carboanion and there is the part of following formula (SA) in part-structure.
[changing 48]
In formula, R dA1represent aryl, R dA2represent alkyl or aryl.R dA1with R dA2also can bond and form ring mutually.LL represents vinyl, acetenyl, arlydene or inferior heteroaryl.A represents the integer of 0 ~ 5.
Group represented by above-mentioned formula (SA) be preferably substituted in be coordinated in metal ions M aromatic hydrocarbon ring or nitrogenous heteroaromatic on, be more preferably and be substituted on nitrogenous heteroaromatic.
In group represented by above-mentioned formula (SA), be preferably R dA1and R dA2be aryl.This aryl also can have substituting group, and this substituting group can enumerate aftermentioned substituting group T.
Aryl can enumerate phenyl, naphthyl etc., is preferably phenyl.
LL is preferably the aromatic hydrocarbon ring of the coordination atom containing part or nitrogenous heteroaromatic and-N (R dA1) (R dA2) nitrogen-atoms via singly-bound or pi-conjugated and bond.
The arlydene of LL can enumerate phenylene, naphthylene etc., and inferior heteroaryl is preferably 5 rings of divalence or 6 rings and containing oxygen atom, sulphur atom, nitrogen-atoms as ring member nitrogen atoms, also can through phenyl ring or heterocycle contracting ring.
The heterocycle of inferior heteroaryl include, for example furan nucleus, thiphene ring, pyrrole ring, pyridine ring, is preferably furan nucleus, thiphene ring.
The vinyl of LL, arlydene, inferior heteroaryl also can have substituting group, and this substituting group can enumerate aftermentioned substituting group T.
In above-mentioned formula (SA), being preferably a is 0 or a is 1 and LL is vinyl, acetenyl, phenylene or inferior heteroaryl, being more preferably a is 0 or a is 1 and LL is phenylene or inferior heteroaryl, and then to be preferably a be 0 or a is 1 and LL is phenylene, the furans cyclic group of divalence, the thiophene cyclic group of divalence, being especially preferably a is 0 or a is 1 and LL is phenylene.
In the present invention, also R is preferably dA1with R dA2mutual bond and form ring.
The ring formed is preferably 5 rings or 6 rings, is more preferably at R dA1with R dA2through the ring of bond when being the situation of aryl.
R dA1with R dA2mutual bond and the ring that formed is preferably following ring.
[changing 49]
Herein, R dA3and R dA4separately represent alkyl.
Moreover above-mentioned ring also can have substituting group, this substituting group can enumerate substituting group T.
The concrete example of the part represented by formula of the present invention (DL) is below shown, but the present invention is not limited to these concrete examples.
[changing 50]
[changing 51]
[changing 52]
[changing 53]
[changing 54]
[changing 55]
[changing 56]
[changing 57]
[changing 58]
[changing 59]
[changing 60]
[changing 61]
[changing 62]
These parts can utilize following methods to synthesize: U.S. Patent Application Publication 2010/0258175A1 specification, Japan Patent No. 4298799 publication, " the international version (Angew.Chem.Int.Ed.) of German applied chemistry " (2011,50th volume, 2054-2058 page) middle method, the method recorded in the list of references enumerated in the document or the method according to these methods recorded.
-ligand L X-
Ligand L X represents monodentate ligand, can enumerate: to be selected from by acyloxy anion, acyl sulfenyl anion, sulfo-acyloxy anion, sulfo-acyl sulfenyl anion, acyl group aminooxy group anion, thiocarbamate anion, dithiocarbamate anion, sulfocarbonate anion, dithiocarbonates anion, trithiocarbonate anion, acyl group anion, thiocyanates anion, isothiocyanates anion, cyanate anion, isocyanates anion, cyano group anion, alkylthio group anion, arylthio anion, anion in the cohort that alkoxy anion and aryloxy anion form or the monodentate ligand of these group coordinations, or be selected from by halogen atom, cyano group, carbonyl, dialkyl ketone, formamide (carbonamide), the anion that thioformamide and thiocarbamide form, monodentate ligand in the cohort of atom or compound (comprising the compound that hydrogen atom in anion is substituted).Moreover when X ligand contains the situation of alkyl, thiazolinyl, alkynyl, alkylidene etc., these groups can be straight-chain and also can be branch-like, can be substituted and also can be unsubstituted.In addition when the situation containing aryl, heterocyclic radical, cycloalkyl etc., these groups can be substituted and also can be unsubstituted, and can be monocycle also can contracting ring.
In the present invention, LX is preferably cyanate anion, isocyanates anion, thiocyanates anion, isothiocyanates anion, selenium cyanate anion, isoselenocyanates anion, be more preferably isocyanates anion, isothiocyanates anion, isoselenocyanates anion, be especially preferably isothiocyanates anion.
-charging neutrality gegenion CI-
CI represent must gegenion to make the gegenion during situation of charging neutrality.Usually, whether pigment is cation or is anion or the metal, part and the substituting group that depend on clean ionic charge in metal complex dye.
Have dissociative base etc. by substituting group, metal complex dye also can dissociate and have negative electrical charge.When this situation, the overall electric charge of metal complex dye utilizes CI and through being adjusted to electric neutrality.
When gegenion CI is the situation of positive gegenion, such as gegenion CI is inorganic or organic ammonium ion (such as tetraalkyl ammonium ion, pyridinium ion etc.), Phosphonium ion (such as four alkane base Phosphonium ions, alkyl triphenyl phosphonium ion etc.), alkali metal ion, metal complex ion or proton.Positive gegenion is preferably inorganic or organic ammonium ion (triethyl ammonium, TBuA ion etc.), proton.
When gegenion CI is the situation of negative gegenion, such as gegenion CI can be inorganic anion and also can be organic anion.Include, for example: hydroxide ion, halide anion (such as fluoride ion, chloride ion, bromide ion, iodide ion etc.), alkyl carboxylic acid radical ion (the acetate ion being substituted or being unsubstituted, trifluoroacetic acid etc.), the aryl carboxylic acid radical ion (benzoate anion ion etc.) being substituted or being unsubstituted, alkyl sulfonate ion (the tosylate ion being substituted or being unsubstituted, trifluoromethanesulfonic acid radical ion etc.), aryl sulfonic acid radical ion (the such as p-methyl benzenesulfonic acid radical ion being substituted or being unsubstituted, p-chlorobenzenesulfonic acid radical ion etc.), aryl disulfonic radical ion (such as 1, 3-benzenedisulfonic acid radical ion, 1, 5-naphthalenedisulfonic acid radical ion, 2, 6-naphthalenedisulfonic acid radical ion etc.), alkyl sulfate ion (such as methyl sulfate etc.), sulfate ion, thiocyanate ion, cross chloranion, tetrafluoroborate ion, hexafluorophosphoric acid ester ion, picric acid (picricacid) radical ion.And then charge balance gegenion also can use ionic polymers or have other pigments with pigment opposite charges, metal complex ion (such as two benzene-1,2-bis-mercaptan nickel (III) etc.) also can be used.Negative gegenion is preferably halide anion, the alkyl carboxylic acid radical ion being substituted or being unsubstituted, the alkyl sulfonate ion being substituted or being unsubstituted, the aryl sulfonic acid radical ion being substituted or being unsubstituted, aryl disulfonic radical ion, cross chloranion, hexafluorophosphoric acid ester ion, be more preferably halide anion, hexafluorophosphoric acid ester ion.
-mX、mY-
MX in formula (I) represents 1 when ligand L D is bidentate ligand, represents 0 when ligand L D is tridentate ligand.
MY represents the integer of 0 ~ 3, is preferably 0 or 1, is more preferably 0.
-metal complex dye of the present invention-
Metal complex dye represented by above-mentioned formula (I) of the present invention is preferably following formula (I-1) or the metal complex dye represented by formula (I-2).
[changing 63]
In formula, M and LX in M and LX and above-mentioned formula (I) is synonymous, Anc1 ~ Anc3, X 1~ X 3, 11 ~ 13, m1 ~ m3, R 1~ R 3, Anc1 ~ Anc3, X in n1 ~ n3 and above-mentioned formula (AL) 1~ X 3, 11 ~ 13, m1 ~ m3, R 1~ R 3, n1 ~ n3 is synonymous.
Ring D, ring E, D 1, D 2, R a1~ R a4and ma1 ~ ma4 and above-mentioned formula (DL-1), the ring D in formula (DL-2), ring E, D 1, D 2, R a1~ R a4and ma1 ~ ma4 is synonymous, preferable range is also identical.
The ring formed by ring D and ring E is preferably pyrazole ring, triazole ring or phenyl ring.
In the present invention, in formula (I-1), part represented by formula (I-2), be preferably the part represented by formula (I-1).
The concrete example of the metal complex dye represented by formula of the present invention (I) is below shown, but the present invention is not limited to these concrete examples.These metal complex dyes exist optical isomer, geometric isomer situation time, can be any one of these isomers, also can be the mixture of these isomers in addition.
Herein, the Me in following concrete example represents methyl, and TMS represents TMS.
[changing 64]
[changing 65]
[changing 66]
[changing 67]
[changing 68]
[changing 69]
[changing 70]
[changing 71]
[changing 72]
[changing 73]
[changing 74]
[changing 75]
[changing 76]
[changing 77]
[changing 78]
[changing 79]
[changing 80]
[changing 81]
[changing 82]
[changing 83]
[changing 84]
[changing 85]
[changing 86]
[changing 87]
In addition to the foregoing, following metal complex dye can be enumerated.
Below, the combination of M, LA, LD, LX, CI, mX and mY in formula (I) is shown in table (table 1).
Such as, following D-317 represents the metal complex dye of following chemical constitution.
[changing 88]
[table 1]
Metal complex dye represented by formula of the present invention (I) can utilize following methods to synthesize: U.S. Patent Application Publication 2010/0258175A1 specification, Japan Patent No. 4298799 publication, " the international version (Angew.Chem.Int.Ed.) of German applied chemistry " (2011,50th volume, 2054-2058 page) middle method, the method recorded in the list of references enumerated in the document or the method according to these methods recorded.
Metal complex dye of the present invention maximum absorption wavelength is in the solution preferably the scope of 300nm ~ 1000nm, is more preferably the scope of 350nm ~ 950nm, is especially preferably the scope of 370nm ~ 900nm.
-conductive support body-
Conductive support body is preferably that supporter self as metal has conductivity or has the glass of conductive film layer or the supporter of plastics on the surface.The supporter of plastics include, for example: the transparent polymer film recorded in the numbered paragraphs 0153 of Japanese Patent Laid-Open 2001-291534 publication.Supporter, except glass and plastics, also can use pottery (Japanese Patent Laid-Open 2005-135902 publication), electroconductive resin (Japanese Patent Laid-Open 2001-160425 publication).In conductive support body, also light-operated (light-management) function can be given by effects on surface, such as also can have record in Japanese Patent Laid-Open 2003-123859 publication by anti-reflective film alternately laminated for the oxidation film of high refraction film and low-refraction, also can have leaded light (light-guide) function recorded in Japanese Patent Laid-Open 2002-260746 publication.
The thickness of conductive film layer is preferably 0.01 μm ~ 30 μm, is more preferably 0.03 μm ~ 25 μm, is especially preferably 0.05 μm ~ 20 μm.
Conductive support body is preferably transparent in fact.What is called is transparent in fact, refers to that the transmissivity of light is more than 10%, is preferably more than 50%, is especially preferably more than 80%.Transparent conductivity supporter is preferably coated with the metal oxide of conductivity on glass or plastics.Metal oxide is preferably tin-oxide, is especially preferably indium-tin-oxide, mixes oxyfluoride.The coating weight of the metal oxide of conductivity is now preferably the every 1m of supporter at glass or plastics 2in be 0.1g ~ 100g.When using the situation of transparent conductivity supporter, preferably make light self-supporting side incident.
-semiconductor microactuator particle-
Semiconductor microactuator particle is preferably the chalcogenide (chalcogenide) (such as oxide, sulfide, selenides etc.) of metal or the particulate of perovskite (perovskite).The chalcogenide of metal preferably can enumerate the oxide, cadmium sulfide, cadmium selenide etc. of titanium, tin, zinc, tungsten, zirconium, hafnium, strontium, indium, cerium, yttrium, lanthanum, vanadium, niobium or tantalum.Perovskite preferably can enumerate strontium titanates, calcium titanate etc.In these, be especially preferably titanium oxide (titanium dioxide (titania)), zinc oxide, tin oxide, tungsten oxide.
The crystalline texture of titanium dioxide can enumerate anatase (anatase) type, brockite (brookite) type or rutile (rutile) type, is preferably Detitanium-ore-type, brookite type.Also titania nanotube (nanotube), nano wire (nanowire), nanometer rods (nanorod) can be mixed in titanium dioxide particle, or be used as semi-conducting electrode.
About the particle diameter of semiconductor microactuator particle, to use the average grain diameter of diameter projected area being converted into bowlder, being preferably primary particle is 0.001 μm ~ 1 μm, and the average grain diameter of dispersion is 0.01 μm ~ 100 μm.The method be coated with by semiconductor microactuator particle in conductive support body can enumerate damp process, dry process, additive method.
Between nesa coating and semiconductor layer (photoreceptor layers), in order to prevent directly contacting caused reverse current by electrolyte with electrode, being preferably and forming against short-circuit layer.In order to prevent optoelectronic pole and the contact to electrode, preferably use distance piece (spacer) or spacer (separator).Preferably in the mode of adsorbable a large amount of pigment, surface area is large for semiconductor microactuator particle.Such as under the state being coated with on supporter by semiconductor microactuator particle, being preferably its surface area is more than 10 times relative to projected area, is more preferably more than 100 times.There is no particular restriction for its upper limit, is generally about 5000 times.Usually, the thickness of the layer containing semiconductor microactuator particle is larger, and the amount of the pigment that per unit area can carry more increases, therefore the absorption efficiency of light uprises, but the diffusion length of the electronics produced increases, therefore also becomes large in conjunction with caused loss (loss) again by electric charge.Preferred thickness as the photoreceptor layers of semiconductor layer looks the purposes of element and different, and typical case is 0.1 μm ~ 100 μm.When being used as the situation of dye-sensitized solar cell, being preferably 1 μm ~ 50 μm, being more preferably 3 μm ~ 30 μm.Semiconductor microactuator particle, also can at the temperature lower calcination 10 minutes ~ 10 hours of 100 DEG C ~ 800 DEG C in order to make particle touch each other coating after on supporter.When the situation using glass as supporter, masking temperature is preferably 60 DEG C ~ 400 DEG C.
Moreover semiconductor microactuator particle is at the every 1m of supporter 2in coating weight be preferably 0.5g ~ 500g, be more preferably 5g ~ 100g.The use amount of pigment is preferably the every 1m of supporter generally 2be 0.01 mM ~ 100 mMs, be more preferably 0.1 mM ~ 50 mMs, be especially preferably 0.1 mM ~ 10 mMs.When this situation, the use amount of metal complex dye of the present invention is preferably set as more than 5mol% (molar percentage).In addition, relative to semiconductor microactuator particle 1g, the adsorbance of pigment to semiconductive particles is preferably 0.001 mM ~ 1 mM, is more preferably 0.1 mM ~ 0.5 mM.By setting as this kind of amount of pigment, the sensitizing effect of semiconductor microactuator particle fully can be obtained.
When above-mentioned pigment is the situation of salt, the gegenion of above-mentioned specific metal complex dye is not particularly limited, and include, for example alkali metal ion or level Four ammonium ion etc.
After making pigment adsorb, the surface of amine to semiconductive particles also can be used to process.Preferred amine can enumerate pyridines (such as 4-tributyl pyridine, polyvinylpyridine) etc.When these amines are the situation of liquid, can directly use also to be dissolvable in water in organic solvent and use.
In photo-electric conversion element of the present invention (such as photo-electric conversion element 10) and dye-sensitized solar cell (such as dye-sensitized solar cell 20), at least use the metal complex dye of the invention described above.
In the present invention, also metal complex dye of the present invention and other pigments can be used.
And pigment can enumerate: the Ru complex compound pigment recorded in Japan Patent JP-A 7-500630 publication (pigment of especially synthesis in example 1 ~ example 19 in page upper right hurdle the 7th, row ~ 7th, the 5th page of hurdle, lower-left the 5th row), the Ru complex compound pigment (pigment of especially synthesis in example 1 ~ example 16 in the 20th page of countdown line 3 ~ 29th page the 23rd row) recorded in Japan Patent spy table 2002-512729 publication, the Ru complex compound pigment (pigment especially recorded in numbered paragraphs 0087 ~ numbered paragraphs 0104) recorded in Japanese Patent Laid-Open 2001-59062 publication, the Ru complex compound pigment (pigment especially recorded in numbered paragraphs 0093 ~ numbered paragraphs 0102) recorded in Japanese Patent Laid-Open 2001-6760 publication, the Ru complex compound pigment (pigment especially recorded in numbered paragraphs 0009 ~ numbered paragraphs 0010) recorded in Japanese Patent Laid-Open 2001-253894 publication, the Ru complex compound pigment (pigment especially recorded in numbered paragraphs 0005) recorded in Japanese Patent Laid-Open 2003-212851 publication, the Ru complex compound pigment (pigment especially recorded in [0067]) recorded in International Publication No. 2007/91525 handbook, the Ru complex compound pigment (pigment especially recorded in numbered paragraphs 0120 ~ numbered paragraphs 0144) recorded in Japanese Patent Laid-Open 2001-291534 publication, the Ru complex compound pigment (pigment especially recorded in numbered paragraphs 0095 ~ numbered paragraphs 0103) recorded in Japanese Patent Laid-Open 2012-012570 publication, the sour cyanines in the side recorded in Japanese Patent Laid-Open 11-214730 publication (squarylium cyanine) pigment (pigment especially recorded in numbered paragraphs 0036 ~ numbered paragraphs 0047), the sour cyanines pigment in the side recorded in Japanese Patent Laid-Open 2012-144688 publication (pigment especially recorded in numbered paragraphs 0039 ~ numbered paragraphs 0046 and numbered paragraphs 0054 ~ numbered paragraphs 0060), the sour cyanines pigment in the side recorded in Japanese Patent Laid-Open 2012-84503 publication (pigment especially recorded in numbered paragraphs 0066 ~ numbered paragraphs 0076 grade), the organic pigment (pigment especially recorded in numbered paragraphs 0017 ~ numbered paragraphs 0021) recorded in Japanese Patent Laid-Open 2004-063274 publication, the organic pigment (pigment especially recorded in numbered paragraphs 0021 ~ numbered paragraphs 0028) recorded in Japanese Patent Laid-Open 2005-123033 publication, the organic pigment (pigment especially recorded in numbered paragraphs 0091 ~ numbered paragraphs 0096) recorded in Japanese Patent Laid-Open 2007-287694 publication, the organic pigment (pigment especially recorded in numbered paragraphs 0030 ~ numbered paragraphs 0034) recorded in Japanese Patent Laid-Open 2008-71648 publication, the organic pigment (pigment especially recorded in [0024]) recorded in International Publication No. 2007/119525 handbook, " the international version (Angew.Chem.Int.Ed.) of German applied chemistry " (the 49th volume, 1st ~ 5 pages (2010)) etc. in record porphyrin (porphyrin) pigment, " the international version (Angew.Chem.Int.Ed.) of German applied chemistry " (the 46th volume, 8358th page (2007)) etc. in record phthalocyanine dye.
And pigment preferably can enumerate Ru complex compound pigment, side's sour cyanines pigment or organic pigment.
By metal complex dye of the present invention and other pigments and situation time, the ratio of the quality of quality/other pigments of metal complex dye of the present invention is preferably 95/5 ~ 10/90, be more preferably 95/5 ~ 50/50, and then be preferably 95/5 ~ 60/40, especially be preferably 95/5 ~ 65/35, most preferably be 95/5 ~ 70/30.
-Charger transfer body layer-
Charger transfer body layer used in photo-electric conversion element of the present invention, for having the layer of the function of the oxysome of pigment being supplemented to electronics, is be arranged at by optoelectronic pole and between electrode (counter electrode).Charger transfer body layer contains electrolyte.Electrolytical example can be enumerated: redox couple is dissolved in the liquid electrolyte of gained in organic solvent, makes redox couple to be dissolved in the liquid of gained in organic solvent and be impregnated in the so-called gel electrolyte in polymer substrate, the fuse salt etc. containing redox couple.In order to improve photoelectric conversion efficiency, be preferably liquid electrolyte.The solvent of liquid electrolyte can use nitrile compound, ether compound, ester compounds etc., is preferably nitrile compound, is especially preferably acetonitrile, methoxypropionitrile.
Redox couple include, for example: iodine and iodide (are preferably iodide salt, iodate ionic liquid, and be preferably lithium iodide, tetrabutylammonium iodide, iodate tetrapropyl ammonium, iodide propyl imidazole) combination, alkyl viologen (alkylviologen) (such as methyl chloride purpurine, bromination hexyl purpurine, benzyl viologen tetrafluoroborate) with the combination of its Reduction Body, polyhydroxy benzenes class (such as hydroquinones, naphtho-hydroquinones etc.) with the combination of its oxysome, the combination (such as the combination of red blood salt and potassium ferrocyanide) of the iron complex of divalent and 3 valencys, the combination etc. of the cobalt complex of divalent and 3 valencys.In these, be preferably the combination of cobalt complex of the combination of iodine and iodide, divalent and 3 valencys.
Wherein, above-mentioned cobalt complex is preferably the complex compound represented by following formula (CC).
Co (LL) ma (X) mbCI formula (CC)
In formula (CC), LL represents bidentate ligand or tridentate ligand.X represents monodentate ligand.Ma represents the integer of 0 ~ 3.Mb represents the integer of 0 ~ 6.CI be must gegenion to make the gegenion during situation of charging neutrality.
CI can enumerate the CI in above-mentioned formula (I).
LL is preferably the part represented by following formula (LC).
[changing 89]
In formula (LC), X lC1and X lC3separately represent carbon atom or nitrogen-atoms.Herein, at X lC1during situation for carbon atom, X lC1double bond (X is shown with the key table of atom N lC1=N), at X lC3during situation for carbon atom, X lC3double bond (X is shown with the key table of atom N lC3=N), at X lC1during situation for nitrogen-atoms, X lC1singly-bound (X is shown with the key table of atom N lC1-N), at X lC3during situation for nitrogen-atoms, X lC3singly-bound (X is shown with the key table of atom N lC3-N).
Z lC1, Z lC2and Z lC3separately represent formation 5 ring or the necessary non-metallic atom cohort of 6 rings.Z lC1, Z lC2and Z lC3also can have substituting group, also can via substituting group with adjacent ring closed loop.Q represents 0 or 1.This substituting group can enumerate aftermentioned substituting group T.Moreover, when q is the situation of 0, be positioned at by Z lC25 rings formed or the bond of 6 rings have X lC3position carbon atom on, bond has hydrogen atom or by Z lC3substituting group beyond the heterocyclic radical formed.
X is preferably halide ion.
Part represented by above-mentioned formula (LC) is more preferably the part represented by following formula (LC-1) ~ formula (LC-4).
[changing 90]
R lC1~ R lC11separately represent substituting group.Q1, q2, q6 and q7 separately represent the integer of 0 ~ 4.Q3, q5, q10 and q11 separately represent the integer of 0 ~ 3.Q4 represents the integer of 0 ~ 2.
In formula (LC-1) ~ formula (LC-4), R lC1~ R lC11represented substituting group include, for example fatty group, aromatic series base, heterocyclic radical etc.Substituent concrete example can be enumerated: alkyl, alkoxyl, alkylthio group, aryl, aryloxy group, arylthio, heterocycle etc.Preference can be enumerated: alkyl (such as methyl, ethyl, normal-butyl, n-hexyl, isobutyl group, second butyl, tributyl, dodecyl, cyclohexyl, benzyl etc.), aryl (such as phenyl, tolyl, naphthyl etc.), alkoxyl (such as methoxyl group, ethyoxyl, isopropoxy, butoxy etc.), alkylthio group (such as methyl mercapto, positive butylthio, just own sulfenyl, 2-ethyl hexyl sulfenyl etc.), aryloxy group (such as phenoxy group, naphthoxy etc.), arylthio (such as thiophenyl, naphthalene sulfenyl etc.), heterocyclic radical (such as 2-thienyl, 2-furyl etc.).
The concrete example with the cobalt complex of the part represented by formula (LC) include, for example following complex compound.
[changing 91]
When using the combination of iodine and iodide as electrolytical situation, be preferably further also with the cationic salt compounded of iodine of nitrogenous aromatic series of 5 rings or 6 rings.
The organic solvent dissolving these redox couples is preferably the polar solvent of aprotic (such as acetonitrile, propylene carbonate, ethylene carbonate, dimethyl formamide, dimethyl sulfoxide (DMSO), sulfolane, 1,3-methylimidazole alkane ketone, 3-methyl oxazolidinone etc.).Polymer for the matrix of gel electrolyte include, for example polyacrylonitrile, polyvinylidene fluoride etc.Fuse salt include, for example: mix poly(ethylene oxide) (polyethyleneoxide) at lithium iodide with other at least one lithium salts (such as lithium acetate, lithium perchlorate etc.), the mobility thus under imparting room temperature etc.The addition of polymer during this situation is 1 quality % ~ 50 quality %.In addition, gamma-butyrolacton also can be made to contain in electrolyte, the diffuser efficiency of iodide ion uprises and conversion efficiency raising thus.
As to the additive in electrolyte, except above-mentioned 4-tributyl pyridine, also can add aminopyridine based compound, benzimidazole based compound, aminotriazole(ATA) based compound and aminothiazole based compound, imidazole compound, amino triazine based compound, urea derivative, amide compound, pyrimidine compound and unazotized heterocycle.
In addition, in order to improve photoelectric conversion efficiency, the method for the moisture controlling electrolyte also can be adopted.The method that the method for optimizing controlling moisture can enumerate controlled concentration or the method that dehydrating agent is coexisted.In order to alleviate the toxicity of iodine, also can use the inclusion compound of iodine and cyclodextrin, also can use the method for supply moisture always.Also cyclic amidines (amidine) can be used in addition, also antioxidant, anti hydrolysis agent, anti-decomposition agent, zinc iodide can be added.
Also fuse salt can be used as electrolyte, and preferred fuse salt can be enumerated: containing imidazoles or triazole type cationic ionic liquid, oxazole system, pyridine system, guanidine (guanidium) be and their combination.Also specific anion can be combined to these cation systems.Also additive can be added to these fuse salts.Also the substituting group of liquid crystal liquid crystal property can be had.In addition, the fuse salt of quarternary ammonium salt system can also be used.
Fuse salt beyond these include, for example: mix poly(ethylene oxide) at lithium iodide with other at least one lithium salts (such as lithium acetate, lithium perchlorate etc.), the mobility thus under imparting room temperature etc.
Making its gelation by adding gelating agent in the electrolyte comprising electrolyte and solvent, electrolyte also can be made to become to be as the criterion solid.Gelating agent can be enumerated: siliceous (Si) compound of the scope that the organic compound that molecular weight is less than 1000, molecular weight are 500 ~ 5000, the organic salt formed by specific acid compound and alkali compounds, sorbitol derivatives, polyvinylpyridine.
In addition, method matrix macromolecule, cross-linked type macromolecule compound or monomer, crosslinking agent, electrolyte and solvent are enclosed in macromolecule can also be adopted.
Matrix macromolecule preferably can be enumerated: have nitrogenous heterocyclic macromolecule and make they and electrophilicity compound react the cross-linking agent of gained in the repetitive of main chain or side chain, there is the macromolecule of triazine structure, there is the macromolecule of urea structure, containing liquid crystal compounds, there is the macromolecule of ehter bond, polyvinylidene fluoride system, methacrylate/acrylic ester, thermosetting resin, cross linking polysiloxane, polyvinyl alcohol (PVA), the inclusion compound of poly-alkane glycol and dextrin etc., be added with containing oxygen or the high molecular system of sulfur-bearing, natural polymer etc.Also can add alkali swelling type macromolecule in them, there is the macromolecule etc. of the compound of the charge transfer complex that can form cation position and iodine in a macromolecule.
Also following system can be used as matrix polymer, and above-mentioned system contains isocyanates more than using two senses as a kind of composition, and the cross-linked polymer reacted with functional groups such as hydroxyl, amino, carboxyls.In addition, the cross-linking method etc. that the metal ion compound more than by the cross-linked polymer of hydrosilane groups and double bond compound gained, poly-sulfonic acid or polycarboxylic acid etc. and divalent is reacted can also be adopted.
Can enumerate with the solvent that can preferably use in above-mentioned quasi-solid electrolytical combination: the mixed solvent containing specific phosphate and ethylene carbonate, there is the solvent etc. of specific relative dielectric constant.Also can make to keep liquid electrolyte solution in solid electrolyte film or hole, its method preferably can enumerate the cloth-like solids such as electroconductive polymer film, fibrous solids, filter.
Can use the solid charge such as p-type semiconductor or hole mobile material transport layer, such as CuI, CuNCS etc. replace above liquid electrolyte and accurate solid electrolyte.In addition, the electrolyte recorded in " nature (Nature) " (the 486th volume, the 487th page (2012) etc.) can also be used.Also organic hole transport material can be used as solid charge transport layer.Hole transmission layer preferably can be enumerated: the electroconductive polymers such as polythiophene, polyaniline, polypyrrole and polysilane and 2 rings have the spiro-compounds that C, Si etc. take the central element of tetrahedral structure, the aromatic amine derivatives such as triarylamine, triphenylene (triphenylene) derivative, nitogen-contained heterocycle derivant, liquid crystal liquid crystal property cyano derivative.
Redox couple becomes the carrier (carrier) of electronics, therefore must concentration to a certain degree.Preferred concentration adds up to more than 0.01mol/L, is more preferably more than 0.1mol/L, is especially preferably more than 0.3mol/L.There is no particular restriction for upper limit during this situation, is generally about 5mol/L.
-coadsorbent-
In photo-electric conversion element of the present invention, be preferably and use coadsorbent in the lump with metal complex dye of the present invention or pigment optionally and also.This kind of coadsorbent preferably has the coadsorbent of more than one acidic groups (being preferably the base of carboxyl or its salt), can enumerate aliphatic acid or have the compound of steroids (steroid) skeleton.Aliphatic acid can be saturated fatty acid and also can be unrighted acid, include, for example: butyric acid, caproic acid, sad, capric acid, hexadecanoic acid, dodecylic acid, palmitic acid, stearic acid, oleic acid, linolenic acid, linolenic acid etc.
The compound with steroid skeleton can be enumerated: cholic acid (cholic acid), glycocholic acid (glycocholic acid), chenodeoxycholic acid (chenodeoxycholic acid), hyocholic acid (hyocholic acid), deoxycholic aicd, lithocholic acid (lithocholicacid), urso (ursodeoxycholic acid) etc.Be preferably cholic acid, deoxycholic aicd, chenodeoxycholic acid, be more preferably chenodeoxycholic acid.
The compound of preferred coadsorbent represented by following formula (CA).
[changing 92]
In formula, R a1represent the substituting group with acidic groups.R a2represent substituting group.NA represents the integer of more than 0.
Acidic groups is synonymous with the group above, and preferable range is also identical.
In these, R a1be preferably the alkyl replaced through carboxyl or sulfo group or their salt, be more preferably-CH (CH 3) CH 2cH 2cO 2h ,-CH (CH 3) CH 2cH 2cONHCH 2cH 2sO 3h.
R a2aftermentioned substituting group T can be enumerated, be wherein preferably alkyl, hydroxyl, acyloxy, alkyl amino carbonyl oxy, aromatic yl aminocarbonyl oxygen base, be more preferably alkyl, hydroxyl, acyloxy.
NA is preferably 2 ~ 4.
Their particular compound can enumerate the compound and illustrative compound that have a steroid skeleton as above-mentioned.
Coadsorbent of the present invention has following effect by being adsorbed in semiconductor microactuator particle: suppress the effect of the association of the non-efficiency of pigment and prevent the effect of the inverted electron transfer to the redox (redox) in electrolyte being from semiconductor microactuator particle surface.The use amount of coadsorbent is not particularly limited, with regard to effectively showing the viewpoint of above-mentioned effect, relative to above-mentioned pigment 1 mole, be preferably 1 mole ~ 200 moles, be more preferably 10 moles ~ 150 moles, be especially preferably 20 moles ~ 50 moles be advisable.
< substituting group T>
In this manual, about the statement of compound (comprising complex compound, pigment), except this compound itself, also for comprising the connotation of its salt, its ion.In addition, about clearly not recording the substituting group (concatenating group and part are also identical) being substituted, being unsubstituted in this specification, refer to that this base can have arbitrary substituting group.Also be synonymous for the compound that this situation is substituted for clearly not recording, be unsubstituted.Preferred substituents can enumerate following substituting group T.
In addition, in this manual, when being only recited as substituent situation simply, can refer to this substituting group T, in addition, when being only recited as each group, such as alkyl, preferable range, the concrete example of the corresponding group of this substituting group T can be applied.
Substituting group T can enumerate following radicals.
Alkyl (is preferably carbon number 1 ~ 20, such as methyl, ethyl, isopropyl, tributyl, amyl group, heptyl, 1-ethyl pentyl group, benzyl, 2-ethoxyethyl group, 1-carboxymethyl group, trifluoromethyl etc.), thiazolinyl (is preferably carbon number 2 ~ 20, such as vinyl, pi-allyl, oleyl etc.), alkynyl (is preferably carbon number 2 ~ 20, such as acetenyl, diacetylene base, phenylene-ethynylene etc.), cycloalkyl (is preferably carbon number 3 ~ 20, such as cyclopropyl, cyclopenta, cyclohexyl, 4-methylcyclohexyl etc.), cycloalkenyl group (is preferably carbon number 5 ~ 20, such as cyclopentenyl, cyclohexenyl group etc.), aryl (is preferably carbon number 6 ~ 26, such as phenyl, 1-naphthyl, 4-methoxyphenyl, 2-chlorphenyl, 3-aminomethyl phenyl etc.), heterocyclic radical (is preferably carbon number 2 ~ 20, is more preferably and has at least one oxygen atom, sulphur atom, 5 rings of nitrogen-atoms or the heterocyclic radical of 6 rings, such as 2-pyridine radicals, 4-pyridine radicals, 2-imidazole radicals, 2-benzimidazolyl, 2-thiazolyl, 2-oxazolyl etc.), alkoxyl (is preferably carbon number 1 ~ 20, such as methoxyl group, ethyoxyl, isopropoxy, benzyloxy etc.), alkene oxygen base (is preferably carbon number 2 ~ 20, such as ethyleneoxy, allyloxy etc.), alkynyloxy group (is preferably carbon number 2 ~ 20, such as 2-propargyl alcoholate, 4-fourth alkynyloxy group etc.), cycloalkyloxy (is preferably carbon number 3 ~ 20, such as ring propoxyl group, cyclopentyloxy, cyclohexyloxy, 4-methyl cyclohexane oxygen base etc.), aryloxy group (is preferably carbon number 6 ~ 26, such as phenoxy group, 1-naphthoxy, 3-methylphenoxy, 4-methoxyphenoxy etc.), heterocyclic oxy group (such as imidazoles oxygen base, benzimidazole oxygen base, thiazole oxygen base, benzothiazole oxygen base, triazine oxy, purine oxygen base),
Alkoxy carbonyl (is preferably carbon number 2 ~ 20, such as ethoxy carbonyl, 2-ethyl hexyl oxy carbonyl etc.), cyclo alkoxy carbonyl (is preferably carbon number 4 ~ 20, such as ring propoxycarbonyl, cyclopentyloxy carbonyl, cyclohexyloxy carbonyl etc.), aryloxycarbonyl (is preferably carbon number 6 ~ 20, such as phenyloxycarbonyl, naphthoxycarbonyl etc.), it is amino that (preferably carbon number 0 ~ 20, comprises alkyl amino, alkenyl amino, alkynylamino, cycloalkyl amino, cycloalkenyl group is amino, arylamino, heterocyclic amino group, such as amino, N, N-dimethylamino, N, N-diethylamino, N-ethylamino, N-allyl amino, N-(2-propynyl) is amino, N-Cyclohexylamino, N-cyclohexenyl group is amino, anilino-, pyridinylamino, imidazole radicals is amino, benzimidazolyl is amino, thiazolyl amino, benzothiazolyl is amino, triazine radical amido etc.), sulfamic (is preferably carbon number 0 ~ 20, is preferably alkyl, the sulfamic of cycloalkyl or aryl, such as N, N-dimethyl amine sulfonyl, N-cyclo-hexylamine sulfonyl, N-phenyl amine sulfonyl etc.), acyl group (is preferably carbon number 1 ~ 20, such as acetyl group, cyclohexyl-carbonyl, benzoyl etc.), acyloxy (is preferably carbon number 1 ~ 20, such as acetoxyl group, cyclohexyl carbonyl oxygen base, benzoyloxy etc.), carbamyl (is preferably carbon number 1 ~ 20, is preferably alkyl, the carbamyl of cycloalkyl or aryl, such as N, N-dimethylcarbamoyl, N-cyclohexyl carbamyl, N-phenylcarbamoyl etc.),
Acyl amino (is preferably the acyl amino of carbon number 1 ~ 20, such as acetyl-amino, cyclohexylcarbonylamino, benzoyl-amido etc.), sulfoamido (is preferably carbon number 0 ~ 20, be preferably alkyl, the sulfoamido of cycloalkyl or aryl, such as amsacrine, benzsulfamide, N-methylmethane sulfonamide, N-cyclohexyl sulfonamide, N-ethyl beneznesulfonamide etc.), alkylthio group (is preferably carbon number 1 ~ 20, such as methyl mercapto, ethylmercapto group, isopropyisulfanyl, benzylthio etc.), cycloalkylthio (is preferably carbon number 3 ~ 20, such as ring rosickyite base, ring penta sulfenyl, cyclohexylthio, 4-methyl cyclohexane sulfenyl etc.), arylthio (is preferably carbon number 6 ~ 26, such as thiophenyl, 1-naphthalene sulfenyl, 3-methylphenyl-sulfanyl, 4-Methoxv-phenylsulfanvl etc.), alkyl, cycloalkyl or aryl sulfonyl (are preferably carbon number 1 ~ 20, such as methyl sulphonyl, ethylsulfonyl, cyclohexylsulfonyl, benzenesulfonyl etc.),
Silylation (is preferably carbon number 1 ~ 20, and is preferably through alkyl, aryl, the silylation that alkoxyl and aryloxy group replace, such as triethyl silyl, tri-phenyl-silane base, diethylbenzyl silylation, dimethylphenylsilaneand base etc.), silicon alkoxyl (is preferably carbon number 1 ~ 20, is preferably through alkyl, aryl, the silicon alkoxyl that alkoxyl and aryloxy group replace, such as triethyl silicane oxygen base, tri-phenyl-silane oxygen base, diethylbenzyl silicon alkoxyl, dimethylphenylsilaneand oxygen base etc.), hydroxyl, cyano group, nitro, halogen atom (such as fluorine atom, chlorine atom, bromine atoms, atomic iodine etc.), carboxyl, sulfo group, phosphono, phosphoryl, boronate, is more preferably alkyl, thiazolinyl, cycloalkyl, aryl, heterocyclic radical, alkoxyl, cycloalkyloxy, aryloxy group, alkoxy carbonyl, cyclo alkoxy carbonyl, above-mentioned amino, acyl amino, cyano group or halogen atom, especially preferably can enumerate alkyl, thiazolinyl, heterocyclic radical, alkoxyl, alkoxy carbonyl, amino, acyl amino or cyano group.
When compound or substituting group etc. are containing alkyl, thiazolinyl etc., they can be straight-chain and also can be branch-like, can be substituted and also can be unsubstituted.In addition, when containing aryl, heterocyclic radical etc., they can be monocycle also can contracting ring, can be substituted and also can be unsubstituted.
< is to electrode (counter electrode) >
Positive pole as dye-sensitized solar cell (photoelectrochemical cell) is preferably to electrode and plays a role.Usually be synonymous with above-mentioned conductive support body to electrode, if but the formation of intensity fully can be kept, then not necessarily supporter.The high structure of current collection effect is preferably to the structure of electrode.In order to make light arrive photoreceptor layers, above-mentioned conductive support body with must be transparent in fact at least one of electrode.In dye-sensitized solar cell of the present invention, preferably conductive support body is transparent and makes sunlight self-supporting side incident.When this situation, electrode is more preferably to the character with reverberation.Dye-sensitized solar cell glass or the plastics that evaporation has the oxide of metal or conductivity are preferably to electrode, being especially preferably evaporation has the glass of platinum.In dye-sensitized solar cell, in order to prevent evapotranspiring of construct, preferably utilize polymer or bonding agent etc. by the side seal of battery.
The present invention can be applicable to photo-electric conversion element, the dye-sensitized solar cell recorded in Japan Patent No. 4260494 publication, Japanese Patent Laid-Open 2004-146425 publication, Japanese Patent Laid-Open 2000-340269 publication, Japanese Patent Laid-Open 2002-289274 publication, Japanese Patent Laid-Open 2004-152613 publication, Japanese Patent Laid-Open 9-27352 publication.In addition, can be applicable to Japanese Patent Laid-Open 2004-152613 publication, Japanese Patent Laid-Open 2000-90989 publication, Japanese Patent Laid-Open 2003-217688 publication, Japanese Patent Laid-Open 2002-367686 publication, Japanese Patent Laid-Open 2003-323818 publication, Japanese Patent Laid-Open 2001-43907 publication, Japanese Patent Laid-Open 2000-340269 publication, Japanese Patent Laid-Open 2005-85500 publication, Japanese Patent Laid-Open 2004-273272 publication, Japanese Patent Laid-Open 2000-323190 publication, Japanese Patent Laid-Open 2000-228234 publication, Japanese Patent Laid-Open 2001-266963 publication, Japanese Patent Laid-Open 2001-185244 publication, Japan Patent spy table 2001-525108 publication, Japanese Patent Laid-Open 2001-203377 publication, Japanese Patent Laid-Open 2000-100483 publication, Japanese Patent Laid-Open 2001-210390 publication, Japanese Patent Laid-Open 2002-280587 publication, Japanese Patent Laid-Open 2001-273937 publication, Japanese Patent Laid-Open 2000-285977 publication, the photo-electric conversion element recorded in Japanese Patent Laid-Open 2001-320068 publication etc., dye-sensitized solar cell.
" pigment solution, use its pigment adsorption electrode and the manufacture method of dye-sensitized solar cell "
In the present invention, be preferably the pigment solution of use containing metal complex dye of the present invention and manufacture pigment adsorption electrode.
This kind of pigment solution is dissolved in solvent by metal complex dye of the present invention to form, and optionally also can contain coadsorbent or other compositions.
The solvent used can enumerate the solvent recorded in Japanese Patent Laid-Open 2001-291534 publication, is not particularly limited.Be preferably organic solvent in the present invention, be more preferably alcohols, amide-type, nitrile, hydro carbons and their two or more mixed solvent.Mixed solvent is preferably alcohols and the mixed solvent being selected from the solvent in amide-type, nitrile or hydro carbons.Be more preferably the mixed solvent of alcohols and amide-type, alcohols and hydro carbons, be especially preferably the mixed solvent of alcohols and amide-type.Specifically, methyl alcohol, ethanol, propyl alcohol, butanols, dimethyl formamide, dimethylacetylamide is preferably.
Pigment solution is preferably containing coadsorbent, and coadsorbent is preferably above-mentioned coadsorbent, is wherein preferably the compound represented by above-mentioned formula (CA).
Herein, pigment solution of the present invention is preferably when manufacturing photo-electric conversion element or dye-sensitized solar cell, have adjusted the concentration of metal complex dye or coadsorbent directly can use the mode of this solution.In the present invention, be preferably the metal complex dye of the present invention containing 0.001 quality % ~ 0.1 quality %.
Pigment solution especially preferably adjusts moisture, therefore, preferably the content (containing ratio) of water is adjusted to 0 quality % ~ 0.1 quality % in the present invention.
In order to effectively play effect of the present invention, also the electrolytical moisture similarly adjusted in photo-electric conversion element or dye-sensitized solar cell is preferably, therefore, preferably the moisture (containing ratio) of this electrolyte is adjusted to 0 quality % ~ 0.1 quality %.This electrolytical adjustment is especially preferably carried out in pigment solution.
In the present invention, the semi-conducting electrode of the dye-sensitized solar cell on preferably use above-mentioned pigment solution that metal complex dye is carried on semiconductor microactuator particle surface that semi-conducting electrode possesses and pigment adsorption electrode.
That is, the composition by above-mentioned pigment solution gained is preferably coated to give by the pigment adsorption electrode of dye-sensitized solar cell has in the conductive support body of semiconductor microactuator particle, makes the said composition after coating harden and make photoreceptor layers.
In the present invention, preferably use the pigment adsorption electrode of this dye-sensitized solar cell, and prepare electrolyte and to electrode, use them to assemble, manufacture dye-sensitized solar cell thus.
[embodiment]
Below, according to embodiment, the present invention is described in more detail, but the present invention is not defined in following explanation and is explained.
Embodiment 1
[synthesis of metal complex dye]
Below, the synthetic method of metal complex dye of the present invention is described in detail, but initial substance, pigment intermediate and synthesis path (synthetic route) are not limited to this.
(synthesis of metal complex dye D-1)
Synthetic metals complex compound pigment D-1 is carried out according to following flow process.
[changing 93]
The synthesis of (i) compound 3
Compound 1 1g, compound 2 2.08g are dissolved in THF (oxolane) 62ml, add Pd (PPh 3) 4after the potash 12.5ml aqueous solution of 371mg and 2N (2 equivalent), at 80 DEG C, react a night.Water 100ml, hexane 40ml, ethyl acetate 60ml is added in the solution of gained, after carrying out separatory extraction, organic layer is concentrated, utilizes silicone tube column chromatography (silica-gel column chromatography) by the thick purified purifying of gained, obtain compound 3 1.59g.
(ii) synthesis of compound 5
Compound 3 1.59g, Trifluoroacetic Acid Ethyl Ester are dissolved in toluene 16ml, add the 3rd fourth potassium oxide 1.27g in a nitrogen environment under ice cooling, 4.At room temperature stir 30 minutes, add saturated aqueous ammonium chloride 40ml and ethyl acetate 40ml, after carrying out separatory extraction, organic layer is concentrated.In the thick purified of gained, add ethanol 19ml, hydrazine monohydrate 305mg, stir after 30 minutes at 90 DEG C, add 12N aqueous hydrochloric acid solution 310 μ l and after stirring 30 minutes, carry out reduced pressure concentration.
Thereafter, add saturated sodium bicarbonate aqueous solution 20ml and ethyl acetate 20ml, after carrying out separatory extraction, organic layer is concentrated, utilize silicone tube column chromatography by the thick purified purifying of gained, obtain compound 5 1.54g.
(iii) synthesis of compound 8
Be dissolved in THF (oxolane) 200ml relative to compound 7 5g by the compound 6 of 2 equivalents, at 0 DEG C, one side stirs one side interpolation the 3rd fourth potassium oxide 4 equivalent in a nitrogen environment, is heated to 70 DEG C and stirs a night.In the solution of gained, drip acetic acid and ethanol superfluously, add ammonium acetate superfluously, at 70 DEG C, stir a night.After reduced pressure concentration, add saturated sodium bicarbonate aqueous solution 100ml and carrene 100ml, after carrying out separatory extraction, organic layer is concentrated, utilize the thick purified of methyl alcohol to gained to carry out recrystallization, obtain compound 8 1.01g.
(iv) synthesis of compound 9
Compound 8 1.0g is dissolved in pyridine 20ml, water 10ml, adds potassinm permanganate in a nitrogen environment, at room temperature stir a night.Sodium thiosulfate solution, sodium hydrate aqueous solution is added in the solution of gained, utilize and filter after the removal of generated manganese dioxide, filtrate concentrated and obtains thick purified, utilizing the thick purified of acetonitrile to gained to carry out recrystallization, obtaining compound 9 620mg.
The synthesis of (v) compound 10
Relative to compound 9 600mg, the piperidines of the cyanoacetic acid of 2 equivalents, 4 equivalents is dissolved in dimethyl formamide (Dimethylformamide, DMF), at 60 DEG C, stirs a night.After reduced pressure concentration, utilize the thick purified of methyl alcohol to gained to carry out recrystallization, obtain compound 10 460mg.
Compound 10
Mass spectrum (Mass Spectrometry, MS) data [M-H] +=329
(vi) synthesis of metal complex dye D-1
The ruthenic chloride of 1.0 equivalents is added hot reflux in ethanol after 5 hours relative to compound 10 450mg, till being cooled to room temperature, then filter, in the residue of gained, add compound 51 equivalent, triethylamine 4 equivalent, stir 2 hours at 110 DEG C in diethylene glycol monoethyl ether 30ml.After reduced pressure concentration, after utilizing the thick purified of acetonitrile to gained to carry out recrystallization, the crystallization of gained is added thermal agitation in ammonium thiocyanate and DMF, carries out reduced pressure concentration, obtain thick purified thus.Itself and tetrabutylammonium (TBAOH) are dissolved in methanol solution in the lump, utilize Sephadex (Sephadex) LH-20 tubing string to carry out purifying.The cut of main stor(e)y is reclaimed after also being concentrated, add trifluoromethanesulfonic acid solution, pH value is adjusted to 3, filter precipitate, obtain metal complex dye D-1 240mg.
(synthesis of metal complex dye D-14)
The part of terpyridyl skeleton is synthesized, below synthetic metals complex compound pigment D-14 in the same manner as metal complex dye D-1 according to following flow process.
[changing 94]
(synthesis of metal complex dye D-18)
The part of terpyridyl skeleton is synthesized, below synthetic metals complex compound pigment D-18 in the same manner as metal complex dye D-1 according to following flow process.
[changing 95]
(synthesis of metal complex dye D-25)
According to following flow process, synthetic metals complex compound pigment D-25 in the same manner as metal complex dye D-1.
[changing 96]
By shown in Figure 3 for the visible absorption spectra of the metal complex dye D-25 of gained.
Measure with the UV-3600 that the concentration of 17 μm of ol/L utilizes limited company of Shimadzu Seisakusho Ltd. to manufacture.
Fig. 3 is mensuration solvent is N, the spectrogram of dinethylformamide (DMF), Fig. 4 measures the spectrogram that solvent is the methanol solution containing 340mmol/L tetrabutylammonium (TBAOH), this spectrum and the TiO being adsorbed with metal complex dye D-25 2the visible absorption spectra of film is close.
(synthesis of metal complex dye D-26)
According to following flow process, synthetic metals complex compound pigment D-26 in the same manner as metal complex dye D-1, metal complex dye D-25.
[changing 97]
Metal complex dye D-26 also utilizes the method for following flow process to synthesize.
[changing 98]
The synthesis of (i) compound 21
Be dissolved in oxolane (THF) 200ml by compound 20 (2-acetyl group-4-picoline) 25g, at 0 DEG C, one side stirs one side interpolation ethoxyquin sodium 18.9g and stirs 15 minutes in a nitrogen environment.Thereafter, drip Trifluoroacetic Acid Ethyl Ester 28.9g, stir 20 hours under outside temperature 70 C.After getting back to room temperature, drip aqueous ammonium chloride solution, carry out separatory, organic layer is concentrated, obtain the thick purified 72.6g of compound 21.
(ii) synthesis of compound 22
Be dissolved in ethanol 220ml by compound 21 72.6g, at room temperature one side stirs one side interpolation hydrazine monohydrate 5.6ml in a nitrogen environment, heats 12 hours at external temperature 90 DEG C.Thereafter, add concentrated hydrochloric acid 5ml, stir 1 hour.After concentrated, utilize sodium bicarbonate water 150ml and ethyl acetate 150ml to carry out extracting, after separatory, organic layer concentrated.After utilizing acetonitrile to carry out recrystallization, obtain compound 22 31.5g.
(iii) synthesis of compound 23
After by diisopropylamine 4.1g and oxolane 30ml, at-40 DEG C, one side stirs one side dropping 1.6M lithium hexane solution 23.1ml in a nitrogen environment, stir 2 hours.Thereafter, add compound 22 4.0g, stir after 80 minutes at 0 DEG C, drip the solution be dissolved in by 2-hexyl thiophene-5-formaldehyde 5.00g in oxolane 15ml.Thereafter, stir 80 minutes at 0 DEG C, at room temperature stir 5 hours.Thereafter add ammonium chloride solution, utilize ethyl acetate to carry out extraction separatory.Organic layer is concentrated, after utilizing silicone tube column chromatography to carry out purifying, obtains compound 23 5.0g.
(iv) synthesis of compound 24
Compound 23 4.9g and para-methylbenzenepyridinsulfonate sulfonate (Pyridinium-p-Toluenesulfonate, PPTS) 4.1g is added in toluene 50ml, carries out in a nitrogen environment adding hot reflux in 5 hours.After concentrated, utilize saturated sodium bicarbonate water and carrene to carry out separatory, organic layer is concentrated.After utilizing methyl alcohol and carrene to carry out recrystallization to the crystallization of gained, obtain compound 24 3.2g.
The synthesis of (v) compound 25
Dichloro (cymene) ruthenium (II) dimer 1.22g, compound 24 1.62g are added in ethanol 150ml, stir 3 hours at 70 DEG C in a nitrogen environment.Thereafter, get back to room temperature, interpolation sodium bicarbonate water, ethyl acetate implement separatory operation, by organic layer reduced pressure concentration.In the crude product of gained, add acetonitrile carry out recrystallization, filter, obtain compound 25 1.5g through super-dry.
For like this compound 25 of synthesis, utilize the compound 27 as part to synthesize compound 28 according to following reaction process, carry out synthetic metals complex compound D-26 via compound 29.
[changing 99]
(vi) synthesis of compound 12
Chloro-for 2,6-bis-4-pyridine carboxaldehyde 4.30g, p-methyl benzenesulfonic acid 1.49g, dehydrated toluene 50ml are put into there-necked flask and stir.Add ethylene glycol 3.0ml wherein, Dien Stark apparatus (Dean-Stark) is set, utilizes the oil bath of 140 DEG C (oil bath) to add hot reflux 6 hours.Get back to room temperature, after slowly dripping 5% sodium bicarbonate water 50ml, operated by separatory and extract organic layer.Toluene 50ml will be added in water layer and the operation carrying out extracting repeats 2 times, organic layer is merged, carries out reduced pressure concentration.Utilize the silicone tube column chromatography using hexane/ethyl acetate as eluent to carry out purifying, obtain compound 12 4.91g.And then, expand its scale (scale) and react, synthesis compound 12 30g.
(vii) synthesis of compound 11
Use 2-bromo-4-pyridine carboxaldehyde 50g, and utilize the synthetic method identical with compound 12 to synthesize compound 11 58.0g.
(viii) synthesis of compound 13
Put into there-necked flask by compound 11 20.71g, dehydrated toluene 400ml, hexa methyl ditin (hexam ethyl ditin) 30.96g, one side stirs one side and carries out nitrogen replacement.Add tetrakis triphenylphosphine palladium 10.4g, utilize the oil bath of 140 DEG C to add hot reflux 2 hours.Thereafter, add compound 12 8.21g, after again implementing nitrogen replacement, add tetrakis triphenylphosphine palladium 10.4g, utilize the oil bath of 140 DEG C to add hot reflux 12 hours.Get back to room temperature, add chloroform 200ml and after implementing ultrasonic wave, carry out diatomite filtration, reduced pressure concentration.Utilize the alumina tube column chromatography using toluene/ethyl acetate as eluent to carry out purifying to it, obtain compound 13 9.09g.The qualification of the compound of gained utilizes 1h-nulcear magnetic resonance (NMR) ( 1h-NMR (nuclear magneticresonance)) and MS spectrum carry out.
Compound 13
MS data [M-H] +=450
Will 1h-NMR spectrum is shown in Figure 29.
(ix) synthesis of compound 26
Compound 13 6.0g, concentrated hydrochloric acid 120ml are put into there-necked flask, utilizes the oil bath of 70 DEG C to add thermal agitation 2 hours.Thereafter, add distilled water 180ml, add thermal agitation 1 hour.Get back to room temperature, drip sodium bicarbonate water 1200ml, generated crystallization is filtered, washes, dry, obtain compound 26 4.18g.The qualification of the compound of gained utilizes 1h-NMR and MS spectrum carries out.
Compound 26
MS data [M-H] +=318
Will 1h-NMR spectrum is shown in Figure 30.
The synthesis of (x) compound 27
Compound 26 2g, dehydration oxolane 200ml are put into there-necked flask, utilizes the oil bath of 95 DEG C to carry out adding thermal agitation.After dissolving completely, add potash 8.72g, diethyl phosphonoacetic acid ethyl ester 7.07g, add hot reflux under a nitrogen 2 hours.Get back to room temperature, add distilled water 600ml, the sediment generated is filtered, washes, dry, obtain compound 27 2.6g.The qualification of the compound of gained utilizes 1h-NMR and MS spectrum carries out.
Compound 27
MS data [M-H] +=528
Will 1h-NMR spectrum is shown in Figure 31.
(xi) synthesis of compound 28
Compound 25 640mg, compound 27 500mg, DMF 10ml are put into there-necked flask, at 130 DEG C, adds thermal agitation 3 hours.Get back to room temperature, add saturated aqueous common salt, ethyl acetate, after implementing separatory operation, by organic layer reduced pressure concentration, utilize silicone tube column chromatography to carry out purifying, obtain compound 28 300mg.
(xii) synthesis of compound 29
Compound 28 200mg, ammonium thiocyanate 142mg, DMF 4ml are put into there-necked flask, at 130 DEG C, adds thermal agitation 2 hours.Get back to room temperature, add saturated aqueous common salt, ethyl acetate, after implementing separatory operation, by organic layer reduced pressure concentration, utilize silicone tube column chromatography to carry out purifying, obtain compound 29 110mg.
(xiii) synthesis of metal complex dye D-26
Compound 29 97mg, DMF 6ml are put into there-necked flask, is cooled to 0 DEG C.One side stirs the 3N sodium hydrate aqueous solution that one side adds excess quantity, stirs 6 hours.Then, add the trifluoromethanesulfonic acid aqueous solution of 1N that adjusts in advance and be adjusted to acid, generated sediment being filtered, washes, dry, obtaining metal complex dye D-2687mg.
The visible absorption spectra of the metal complex dye D-26 of gained is shown in Fig. 5, Fig. 6.
In the same manner as metal complex dye D-25, the UV-3600 utilizing limited company of Shimadzu Seisakusho Ltd. to manufacture measures the methanol solution containing 340mmol/L tetrabutylammonium (TBAOH) with the concentration of 17 μm of ol/L, by shown in Figure 5 for the visible absorption spectra of gained.In addition, by shown in Figure 6 for the visible absorption spectra making the semiconductor film (being adsorbed with the oxidation titanium film of metal complex dye D-26) of model according to the specimen coding 102 in aftermentioned embodiment 4.
The visible absorption spectra (Fig. 5) learning the methanol solution containing 340mmol/L tetrabutylammonium (TBAOH) is similar with the visible absorption spectra (Fig. 6) of the oxidation titanium film being adsorbed with metal complex dye D-26.
(synthesis of metal complex dye D-28)
Synthetic metals complex compound pigment D-28 in the same manner as metal complex dye D-1, metal complex dye D-25, metal complex dye D-26.
[changing 100]
(synthesis of metal complex dye D-45)
Synthetic metals complex compound pigment D-45 in the same manner as metal complex dye D-1, metal complex dye D-25, metal complex dye D-26.
[changing 101]
(synthesis of metal complex dye D-57)
In 50ml eggplant type flask, add the metal complex dye D-28 100mg, the THF 10ml that synthesize as described above, one side stirs the tetrabutylammonium that one side interpolation is 1 equivalent relative to metal complex dye D-28, at room temperature stirs 30 minutes.Thereafter, solvent under reduced pressure distillation is removed, carries out drying, obtain metal complex dye D-57 thus.The qualification of compound utilizes substance assistant laser desorpted ionized-mass spectrography (Matrix-assisted laser desorption ionization-MassSpectrometry, MALDI-MS) to carry out.
[changing 102]
(synthesis of metal complex dye D-59)
According to following flow process, synthetic metals complex compound pigment D-59 in the same manner as metal complex dye D-1, metal complex dye D-25, metal complex dye D-26.
[changing 103]
Moreover, the MS spectrum of compound 14 is below shown.
Compound 14
MS data [M-H] +=612
(synthesis of metal complex dye D-62)
Compound 34 is synthesized, synthetic metals complex compound pigment D-62 in the same manner as metal complex dye D-26, metal complex dye D-59 according to following flow process.
[changing 104]
Moreover, the MS spectrum of compound 31 ~ compound 34 is below shown.
Compound 31
MS data [M-H] +=450
Compound 32
MS data [M-H] +=334
Compound 33
MS data [M-H] +=474
Compound 34
MS data [M-H] +=502
Will 1h-NMR spectrum is shown in Figure 32.
(synthesis of metal complex dye D-78)
Using compound 50 as initial substance, utilize and " heterocyclic chemistry periodical (J.Heterocycl.Chem.) " (2008,45th volume, 91st ~ 96 pages) in the identical method of method recorded synthesize compound 51 ~ compound 53, then use compound 53 and compound 30 to carry out history Supreme Being and strangle (Stille) coupling, obtain compound 54 thus.The qualification of the compound of gained utilizes electron spray ionisation-mass spectrography (Electrospray Ionization Mass Spectrometry, ESI-MS) to carry out.Use compound 54, synthetic metals complex compound pigment D-78 in the same manner as aftermentioned metal complex dye D-141.The qualification of compound utilizes ESI-MS to carry out.
[changing 105]
Moreover, the MS spectrum of compound 54 is below shown.
Compound 54
MS data [M-H] +=562
(synthesis of metal complex dye D-97)
In the same manner as metal complex dye D-26, metal complex dye D-59, carry out synthetic metals complex compound pigment D-97 according to following flow process.
[changing 106]
The synthesis of (i) compound 53
Compound 53 is synthesized according to the method recorded in " Bioorganic Chemistry and medical chemistry communication (Bioorg.Med.Chem.Lett.) " (the 17th volume, 2401st ~ 2403 pages (2007)).
(ii) synthesis of compound 54
Utilize and " Bioorganic Chemistry and medical chemistry communication (Bioorg.Med.Chem.Lett.) " (the 17th volume, 2401st ~ 2403 pages (2007)) in the identical method of method recorded, use compound 53 and two carbonic acid two-tributyls to synthesize compound 54.
(iii) synthesis of compound 55
Compound 26 1g, compound 54 7.22g, DMF (dehydration) 8ml are put into 20ml eggplant type flask, utilizes the oil bath of 140 DEG C to add thermal agitation 1.5 hours.Get back to room temperature, after solvent under reduced pressure distillation is removed, utilize silicone tube column chromatography to carry out purifying, and then utilize gel permeation chromatography (Gel Permeation Chromatography, GPC) to carry out purifying, obtain compound 55 800mg thus.
Moreover, the MS spectrum of compound 55 is below shown.
Compound 55
MS data [M-H] +=858
(iv) synthesis of metal complex dye D-97
Use compound 55, utilize the method identical with D-26 to synthesize compound 57.Compound 57 370mg, carrene 50ml, trifluoroacetic acid 2ml are put into 100ml there-necked flask, stirs 2.5 hours.Thereafter, add carrene 25ml, trifluoroacetic acid 3ml and after stirring 1.5 hours, add carrene 100ml, trifluoroacetic acid 10ml and stir 2 hours at 30 DEG C, and then add trifluoroacetic acid 8ml and stir 2 hours at 30 DEG C.Get back to room temperature, solvent under reduced pressure distillation is removed, utilizes methyl alcohol to disperse, sediment is filtered.Utilize methyl alcohol, water cleans, implement dry, obtain D-97 283mg thus.
(synthesis of metal complex dye D-101)
Synthetic metals complex compound pigment D-101 is carried out in the same manner as metal complex dye D-26, metal complex dye D-59, metal complex dye D-97.
[changing 107]
Moreover, the MS spectrum of the following compound 15 of the intermediate raw material as metal complex dye D-101 is below shown.Herein, compound 15 utilizes the method according to compound 55 to synthesize.
[changing 108]
Compound 15
MS data [M-H] +=756
(synthesis of metal complex dye D-136)
Compound 41 is synthesized, synthetic metals complex compound pigment D-136 in the same manner as metal complex dye D-26, metal complex dye D-59 according to following flow process.
[changing 109]
The synthesis of (i) compound 37
Compound 20 10g, ethylene glycol 8.24ml, p-methyl benzenesulfonic acid monohydrate 4.22g, dehydrated toluene 200ml are put into there-necked flask, at 140 DEG C, adds thermal agitation 5 hours.Get back to room temperature, add sodium bicarbonate water, toluene, implement separatory operation, by organic layer reduced pressure concentration.Utilize the silicone tube column chromatography using hexane/ethyl acetate as eluent to carry out purifying, obtain compound 37 11.78g.
(ii) synthesis of compound 38
Diisopropylamine 12.89g, dehydration oxolane (THF) 60ml are put into the there-necked flask through nitrogen replacement, is cooled to-60 DEG C.Slowly drip n-BuLi 72ml, stir 30 minutes.After slowly dripping diisopropylamine 188ml, be warming up to-50 DEG C, drip the solution being dissolved with 9.85g compound 37 in oxolane 5ml.Thereafter, be warming up to 0 DEG C, drip the solution being dissolved with the bromo-2-ethyl hexane of 23.4g 1-in oxolane 45ml, stir 2 hours.Add aqueous ammonium chloride solution 100ml, implement separatory operation, by organic layer reduced pressure concentration.Utilize the silicone tube column chromatography using hexane/ethyl acetate as eluent to carry out purifying, obtain compound 38 7.3g.
(iii) synthesis of compound 39
Compound 38 6.60g, concentrated hydrochloric acid 25ml are put into there-necked flask, at 90 DEG C, adds thermal agitation 30 minutes.Get back to room temperature, reactant liquor is slowly dropped in sodium bicarbonate water, add ethyl acetate 200ml.By organic layer reduced pressure concentration, obtain compound 39 5.73g.
(iv) synthesis of compound 41
Compound 39 5.73g, Trifluoroacetic Acid Ethyl Ester 7.61g, dehydrated toluene 100ml are put into there-necked flask, at room temperature stirs and add the 3rd butoxy potassium 5.44g simultaneously and stir 1 hour.Add saturated aqueous ammonium chloride 100ml, ethyl acetate 20ml, implement separatory operation, organic layer is concentrated.Add ethanol, hydrazine monohydrate 1.50g wherein, at 90 DEG C, add hot reflux 1 hour.Add hydrochloric acid 7ml, distilled water 200ml, ethyl acetate 200ml, implement separatory operation, organic layer is slowly dropped in sodium bicarbonate water 200ml.Enforcement separatory operates, and utilizes the silicone tube column chromatography using hexane/ethyl acetate as eluent to carry out purifying, obtains compound 41 6.04g.
(synthesis of metal complex dye D-140)
Compound 45 is synthesized, synthetic metals complex compound pigment D-140 in the same manner as metal complex dye D-26, metal complex dye D-59 according to following flow process.
[changing 110]
The synthesis of (i) compound 42
3rd fourth sodium oxide molybdena 2.47g, dimethylbenzene 25ml, 4-Amino-2-Chloropyridine 1.5g, 4-iodine amylbenzene 9.60g are put into there-necked flask, carries out nitrogen replacement.One side stirs one side interpolation three (dibenzalacetone) two palladium (0) 0.534g, three-tributylphosphine 0.472g, adds hot reflux 2 hours.Get back to room temperature, add frozen water, ethyl acetate, by organic layer reduced pressure concentration.Utilize the silicone tube column chromatography using hexane/ethyl acetate as eluent to carry out purifying, obtain compound 42 3.7g.
(ii) synthesis of compound 44
Will according to " organic chemistry periodical (J.Org.Chem.) " (2008,73rd volume, 4309-4312 page) in record method synthesis compound 43 2.66g, compound 42 2.70g, tri-potassium phosphate 5.45g, 1,2-dimethoxy-ethane 54ml puts into there-necked flask, carries out nitrogen replacement.One side stirs one side and adds Xphos GIII 0.54g, adds hot reflux 3 hours.Get back to room temperature, implement diatomite filtration, after solvent under reduced pressure distillation is removed, utilize the silicone tube column chromatography using hexane/ethyl acetate as eluent to carry out purifying, obtain compound 44 1.82g.
(iii) synthesis of compound 45
Compound 44 1.70g, hydrochloric acid/ethyl acetate solution 28ml are put into there-necked flask, stirs 1 hour.Thereafter, add sodium bicarbonate water, implement separatory operation, organic layer is concentrated.Reduce pressure at 140 DEG C, obtain compound 45 3.7g thus.
(synthesis of metal complex dye D-141)
According to following flow process, synthesize compound 49 in the same manner as D-45, synthetic metals complex compound pigment D-141 in the same manner as metal complex dye D-140.
[changing 111]
(synthesis of metal complex dye D-188)
According to following flow process, synthetic metals complex compound pigment D-188 in the same manner as metal complex dye D-140.
[changing 112]
The synthesis of (i) compound 47
By 2-chlorine-4-iodine pyridine 15.0g, compound 46 20.5mL, potash 26.0g, dichloride-1,1 '-bis-(diphenylphosphino) ferrocene-palladium (II)-dichloromethane complex 5.1g, THF 150mL, pure water 150mL puts into the there-necked flask to 500mL, adds hot reflux in a nitrogen environment 3 hours.Make the solution of gained get back to room temperature, utilize ammonium chloride to neutralize, utilize ethyl acetate to extract.Organic layer is concentrated, utilizes silicone tube column chromatography to carry out purifying, obtain compound 47 13g thus.
(ii) synthesis of compound 49
Compound 47 5.0g, potassium phosphate 15.2g, THF 45mL, pure water 45mL, acid chloride 0.2g, S-Phos 0.88g, compound 48 5.83g are put into the there-necked flask to 200mL, add hot reflux in a nitrogen environment 3 hours.Make the solution of gained get back to room temperature, utilize ammonium chloride to neutralize, utilize ethyl acetate to extract.Organic layer is concentrated, utilizes silicone tube column chromatography to carry out purifying, obtain compound 49 3.8g thus.
(iii) synthesis of compound 50
Compound 27 0.73g, ruthenic chloride 0.38g, ethanol 15mL are put into the there-necked flask to 100mL, add hot reflux in a nitrogen environment 4 hours.The sediment of gained is filtered, utilizes ethanol to clean, obtain compound 50 0.96g thus.
(iv) synthesis of compound 51
Compound 50 0.2g, compound 46 0.11g, DMF 20mL, tri-n-butylamine 0.25g are put into there-necked flask, heats 1 hour at 100 DEG C in a nitrogen environment.After getting back to room temperature, concentrate, utilize silicone tube column chromatography to carry out purifying, obtain compound 51 0.18g thus.
The synthesis of (v) compound 52
The mixture of compound 51 0.17g, ammonium thiocyanate 16mg, DMF 14.5mL, pure water 1.5mL is put into the glass container to 5mL, at 160 DEG C, utilizes microwave (microwave) to heat 10 minutes.The solution of gained is concentrated, utilizes silicone tube column chromatography to carry out purifying, obtain compound 52 0.1g thus.
(vi) synthesis of metal complex dye D-188
The NaOH aqueous solution 0.1mL of compound 52 80mg, DMF 3mL, 0.3N is put into the eggplant type flask to 10mL, reacts in ice bath.Utilize TfOH that the pH value of the solution of gained is adjusted to 2.9, filter, clean with ultra-pure water, obtain metal complex dye D-188 60mg.The qualification of compound utilizes MALDI-MS to carry out.
(synthesis of metal complex dye D-280)
In 50ml eggplant type flask, add metal complex dye D-62 100mg, THF 10ml, one side stirs the tetrabutylammonium that one side interpolation is 1 equivalent relative to D-62, at room temperature stirs 30 minutes.Thereafter, solvent under reduced pressure distillation is removed, carries out drying, obtain metal complex dye D-280 thus.The qualification of compound utilizes MALDI-MS to carry out.
Metal complex dye D-280
MS data [M-H] +=956
[changing 113]
In the metal complex dye synthesized as described above, the visible absorption spectra of metal complex dye D-28, metal complex dye D-45, metal complex dye D-57, metal complex dye D-59, metal complex dye D-62, metal complex dye D-97, metal complex dye D-101, metal complex dye D-136, metal complex dye D-140, metal complex dye D-141, metal complex dye D-187, metal complex dye D-188 and metal complex dye D-280 is shown in Fig. 7 ~ Figure 28.
Mensuration is that the UV-3600 utilizing limited company of Shimadzu Seisakusho Ltd. to manufacture in the same manner as metal complex dye D-25, metal complex dye D-26 carries out.
Fig. 7 is the visible absorption spectra of the DMF solution of metal complex dye D-28, and Fig. 8 is the visible absorption spectra of the model semiconductor film of metal complex dye D-28.Fig. 9 is the visible absorption spectra of metal complex dye D-45 under the concentration of 17 μm of ol/L, in the methanol solution containing 340mmol/L tetrabutylammonium (TBAOH), Figure 10 is the visible absorption spectra of metal complex dye D-59 under the concentration of 17 μm of ol/L, in the methanol solution containing 340mmol/L tetrabutylammonium (TBAOH).Figure 11 is the visible absorption spectra of the DMF solution of metal complex dye D-62, Figure 12 is the visible absorption spectra of the model semiconductor film of metal complex dye D-62, Figure 13 is the visible absorption spectra of the DMF solution of metal complex dye D-97, Figure 14 is the visible absorption spectra of the model semiconductor film of metal complex dye D-97, Figure 15 is the visible absorption spectra of the DMF solution of metal complex dye D-101, Figure 16 is the visible absorption spectra of the model semiconductor film of metal complex dye D-101, Figure 17 is the visible absorption spectra of the DMF solution of metal complex dye D-136, Figure 18 is the visible absorption spectra of the model semiconductor film of metal complex dye D-136, Figure 19 is the visible absorption spectra of the DMF solution of metal complex dye D-140, Figure 20 is the visible absorption spectra of the model semiconductor film of metal complex dye D-140, Figure 21 is the visible absorption spectra of the DMF solution of metal complex dye D-141, Figure 22 is the visible absorption spectra of the model semiconductor film of metal complex dye D-141, Figure 23 is the visible absorption spectra of the DMF solution of metal complex dye D-187, Figure 24 is the visible absorption spectra of the model semiconductor film of metal complex dye D-187, Figure 25 is the visible absorption spectra of the DMF solution of metal complex dye D-188, Figure 26 is the visible absorption spectra of the model semiconductor film of metal complex dye D-188, Figure 27 is the visible absorption spectra of the model semiconductor film of metal complex dye D-57, Figure 28 is the visible absorption spectra of the model semiconductor film of metal complex dye D-280.
With metal complex dye D-25, metal complex dye D-26, metal complex dye D-59 similarly, synthetic metals complex compound pigment D-2 ~ metal complex dye D-4, metal complex dye D-7, metal complex dye D-9, metal complex dye D-12, metal complex dye D-16, metal complex dye D-17, metal complex dye D-24, metal complex dye D-27, metal complex dye D-29, metal complex dye D-35, metal complex dye D-48, metal complex dye D-61, metal complex dye D-91, metal complex dye D-96, metal complex dye D-121, metal complex dye D-132, metal complex dye D-142 ~ metal complex dye D-150, metal complex dye D-155, metal complex dye D-187, metal complex dye D-189, metal complex dye D-200, metal complex dye D-241, metal complex dye D-242, metal complex dye D-297.
The structure of the illustration metal complex dye of gained utilizes MS (mass spectrum) to measure to confirm.
The measurement result of mass spectrum (MS) is shown in following table 2.
[table 2]
Metal complex dye ESI-MS or MALDI-MS
D-1 ESI-MSm/z＝867(M-H) +
D-2 ESI-MS m/z＝867(M-H) +
D-3 ESI-MS m/z＝877(M-H) +
D-4 ESI-MS m/z＝893(M-H) +
D-7 ESI-MS m/z＝845(M-H) +
D-9 ESI-MS m/z＝942(M-H) +
D-12 ESI-MS m/z＝944(M-H) +
D-14 ESI-MS m/z＝962(M-H) +
D-16 ESI-MS m/z＝1115(M-H) +
D-17 ESI-MS m/z＝1037(M-H) +
D-18 ESI-MS m/z＝1201(M-H) +
D-24 ESI-MS m/z＝1056(M-H) +
D-25 ESI-MS m/z＝1223(M-H) +
D-26 ESI-MS m/z＝1008(M-H) +
D-27 ESI-MS m/z＝982(M-H) +
D-28 ESI-MS m/z＝982(M-H) +
D-29 ESI-MS m/z＝1082(M-H) +
D-35 ESI-MS m/z＝1033(M-H) +
D-45 ESI-MS m/z＝1148(M-H) +
D-48 ESI-MS m/z＝1044(M-H) +
D-57 MALDI-MS m/z＝982(M-H) +、242(M +)
D-59 ESI-MS m/z＝1092(M-H) +
D-61 ESI-MS m/z＝982(M-H) +
D-62 ESI-MS m/z＝956(M-H) +
D-78 ESI-MS m/z＝1157(M-H) +
D-91 MALDI-MS m/z＝1061(M-H) +
D-96 ESI-MS m/z＝961(M-H) +
D-97 ESI-MS m/z＝1054(M-H) +
D-101 ESI-MS m/z＝1236(M-H) +
D-121 ESI-MS m/z＝1145(M-H) +
D-132 ESI-MS m/z＝1034(M-H) +
D-136 ESI-MS m/z＝942(M-H) +
D-140 ESI-MS m/z＝1123(M-H) +
D-141 ESI-MS m/z＝1123(M-H) +
D-142 ESI-MS m/z＝1171(M-H) +
D-143 ESI-MS m/z＝1171(M-H) +
D-144 ESI-MS m/z＝1097(M-H) +
D-145 ESI-MS m/z＝1097(M-H) +
D-146 ESI-MS m/z＝1145(M-H) +
D-147 ESI-MS m/z＝1145(M-H) +
D-148 ESI-MS m/z＝1093(M-H) +
D-149 ESI-MS m/z＝1093(M-H) +
D-150 ESI-MS m/z＝1141(M-H) +
D-155 ESI-MS m/z＝999(M-H) +
D-187 MALDI-MS m/z＝1060(M-H) +
D-188 MALDI-MS m/z＝992(M-H) +
D-189 ESI-MS m/z＝993(M-H) +、242(M +)
D-200 MALDI-MS m/z＝966(M-H) +
D-241 MALDI-MS m/z＝1224(M-H) +
D-242 MALDI-MS m/z＝1224(M-H) +
D-280 MALDI-MS m/z＝956(M-H) +、242(M +)
D-297 MALDI-MS m/z＝1050(M-H) +
The metal complex dye other than the above below used also is utilize the method identical with these pigments to synthesize.
Embodiment 2
[dye-sensitized solar cell]
As following, make dye-sensitized solar cell, measure the IPCE (quantum yield) under 900nm.
According to order shown below, make and there is the optoelectronic pole with the identical formation of optoelectronic pole 12 shown in the Fig. 5 recorded in Japanese Patent Laid-Open 2002-289274 publication, and then, use optoelectronic pole, make the dye-sensitized solar cell 20 of 10mm × 10mm specification (scale) with the dye-sensitized solar cell 20 in Fig. 3 of this publication except optoelectronic pole with identical formation.Be appended hereto specifically forming to be shown in Fig. 2 of the application.
In Fig. 2 of the application, 41 is transparency electrode, and 42 is semi-conducting electrode, and 43 is nesa coating, and 44 is substrate, and 45 is semiconductor layer, and 46 is light scattering layer, and 40 is optoelectronic pole, and 20 is dye-sensitized solar cell, and CE is to electrode, and E is electrolyte, and S is distance piece.
(preparation of paste (paste))
(paste A) is by spherical TiO 2(anatase, average grain diameter: 25nm, hereinafter referred to as spherical TiO for particle 2particle A) put into salpeter solution and stir, prepare titania slurry thus.Then, in titania slurry, add the cellulose-based adhesive as thickener, carry out mixing and preparing paste.
(paste 1) is by spherical TiO 2particle A and spherical TiO 2(anatase, average grain diameter: 200nm, hereinafter referred to as spherical TiO for particle 2particle B) put into salpeter solution and stir, prepare titania slurry thus.Then, in titania slurry, add the cellulose-based adhesive as thickener, carry out mixing and preparing paste (TiO 2the quality of particle A: TiO 2quality=30 of particle B: 70).
(paste 2) mixes bar-shaped TiO in paste A 2(aspect ratio: 5, hereinafter referred to as bar-shaped TiO for anatase, diameter: 100nm for particle 2particle C), prepare bar-shaped TiO 2the quality of particle C: quality=30 of paste A: the paste of 70.
(making of optoelectronic pole)
Prepare to be formed with the SnO mixing fluorine on glass substrate (44) 2the transparency electrode 41 of conducting film 43 (thickness: 500nm).Then, at this SnO 2screen painting aforesaid paste 1 on conducting film, carries out drying then.Thereafter, calcine under the condition of 450 DEG C in atmosphere.And then, use paste 2 to repeat this screen painting and calcining, thus at SnO 2conducting film is formed the semi-conducting electrode (area of sensitive surface: 10mm × 10mm with the identical formation of semi-conducting electrode 42 shown in Fig. 2, thickness: 15 μm, the thickness of semiconductor layer: 10 μm, the thickness of light scattering layer: 5 μm, the bar-shaped TiO contained by light scattering layer 2the containing ratio of particle C: 30 quality %), make the optoelectronic pole of not containing metal complex compound pigment.
(pigment absorption)
Then, on the optoelectronic pole making metal complex dye be adsorbed in as described below to make as described above.
First, using the absolute ethyl alcohol that dewaters through ethoxyquin magnesium as solvent, 3 × 10 are become with concentration wherein -4the mode of mol/L dissolves the metal complex dye recorded in aftermentioned table 3, and then, add as coadsorbent relative to metal complex dye 1 mole be the chenodeoxycholic acid of 20 moles and cholic acid etc. molar mixture, prepare each pigment solution.Utilize Ka Er-Fischer (Karl-Fisher) titration to measure amount of moisture to this pigment solution, result water is less than 0.01 quality %.Then, in this solution, flood above-mentioned made semi-conducting electrode, be formed in absorption on semi-conducting electrode 42 thus and have an appointment 1.5 × 10 -7mol/cm 2the optoelectronic pole (40) of metal complex dye.
Then, preparation is as the platinum electrode (thickness of Pt film: 100nm) with the shape identical with above-mentioned optoelectronic pole (40) and size to electrode CE, the iodine system redox solution containing iodine and lithium iodide as electrolyte E.And then, prepare that there is the distance piece S (trade name: " sarin (Surlyn) ") manufactured with Du Pont (Dupont) company of the shape of the same size of semi-conducting electrode 42, as recorded as shown in Figure 3 in Japanese Patent Laid-Open 2002-289274 publication, make optoelectronic pole (40) relative with to electrode Jie CE compartment spacing body S, fill above-mentioned electrolyte in inside and make the dye-sensitized solar cell using optoelectronic pole.
The IPCE determinator utilizing Parker Sai Er (Peccell) company to manufacture measures the IPCE of each dye-sensitized solar cell under 300nm ~ 1000nm (quantum yield) so made like that.
Wherein, the IPCE under 900nm is shown in aftermentioned table 3.
Metewand
IPCE under A:900nm is more than 1.1 times of comparative compound (3)
IPCE under B:900nm is greater than 1.0 times of comparative compound (3), is less than 1.1 times of comparative compound (3)
IPCE under C:900nm is 1.0 times of comparative compound (3)
IPCE under D:900nm is less than 1.0 times of comparative compound (3)
Embodiment 3
Evaluate the absorption stability of metal complex dye as described below.
As the evaluation of metal complex dye to the absorption stability (absorption affinity) of semiconductive particles sub-surface, use titanium dioxide as semiconductor microactuator particle, using the metal complex dye desorption rate from this titanium dioxide surface as index.
The desorption rate of metal complex dye utilizes monitoring QCM (Quartz Crystal Microbalance) (Quartz Crystal microbalancewith Dissipation monitoring, QCM-D) the intermolecular interaction determinator E1 that dissipates (alliance and business society (Meiwafosis) limited company manufacture) to calculate.
Golden transducer (alliance and business society (Meiwafosis) limited company manufacture) used in QCM-D utilize screen painting to print aforesaid paste A (anatase, average grain diameter: 25nm) (thickness: 20 μm).Golden transducer through printing is calcined 1 hour in atmosphere at 450 DEG C, makes the golden transducer through semiconductor layer absorption thus.
By made sensor setting in QCM-D intermolecular interaction determinator, the pigment solution (DMF/t-BuOH=1/1) of circulation 0.2mM, makes pigment to become set value (200 μ g/cm thus 2) mode be adsorbed on semiconductor layer.Pigment adsorbance is resonant frequency shift (Δ F) according to quartz crystal unit and utilizes the following Er Bulai of continuing (Sauerbrey) formula to calculate.
ΔF＝-2×F 0 2×Δm/A(μ×p) 1/2
Herein, F 0represent the frequency that quartz crystal unit is independent, Δ m represents mass change, and A represents the piezoelectric activity area of Au electrode, μ and P represents density and the modulus of rigidity of crystal respectively.
Thereafter, 75 DEG C of current downflow 1 hour in above-mentioned electrolyte E, the desorption quantity of pigment is measured thus.Desorb amount of pigment is also utilize Er Bulai (Sauerbrey) formula that continues to calculate, and judges according to following metewand.
Metewand
A: desorption rate is less than 10 μ g/cm 2hr
B: desorption rate is 10 μ g/cm 2more than hr ~ be less than 15 μ g/cm 2hr
C: desorption rate is 15 μ g/cm 2more than hr ~ be less than 20 μ g/cm 2hr
D: desorption rate is 20 μ g/cm 2more than hr ~ be less than 25 μ g/cm 2hr
E: desorption rate is 25 μ g/cm 2more than hr ~ be less than 30 μ g/cm 2hr
F: desorption rate is 30 μ g/cm 2more than hr ~ be less than 35 μ g/cm 2hr
G: desorption rate is 35 μ g/cm 2more than hr
Herein, above-mentioned metewand A ~ metewand E is qualified level.
The result of the above results and embodiment 2 is gathered in the lump and is shown in following table 3.
[table 3]
Metal complex dye IPCE under 900nm Absorption stability
D-1 A D
D-2 A D
D-3 A D
D-4 A D
D-7 A D
D-9 A D
D-12 A D
D-14 A B
D-16 A C
D-17 A B
D-18 A C
D-24 A A
Comparative compound (1) D F
Comparative compound (2) D G
Comparative compound (3) C (benchmark) G
Comparative compound (4) D G
[changing 114]
Herein, the metal complex dye that comparative compound (3) is metewand synthesizes in the same manner as the metal complex dye of the invention described above.
The compound 9 of comparative compound (1) for recording in Japan Patent spy table 2011-502187 publication, comparative compound (2) Compound D-11 for recording in Japanese Patent Laid-Open 2002-105346 publication, comparative compound (4) compound for recording in Japanese Patent Laid-Open 2001-502965 publication.
Clearly learnt by table 3, it is high and have the pigment of absorption stability concurrently that metal complex dye of the present invention is IPCE under the long wavelength of 900nm.
Embodiment 4
[dye-sensitized solar cell]
As following, make dye-sensitized solar cell, carry out the evaluation as photoelectric conversion efficiency and durability of heat deterioration under uniform temperature and thermal cycling test.
The dye-sensitized solar cell 1 of the specification of the 10mm × 10mm of the formation shown in Fig. 2 of present specification is appended hereto with the sequentially built identical with embodiment 2.
In addition, the paste used uses preparation in embodiment 2.
(making of optoelectronic pole)
Prepare to be formed with the SnO mixing fluorine on the glass substrate 2the transparency electrode of conducting film (thickness: 500nm).Then, at this SnO 2screen painting aforesaid paste 1 on conducting film, carries out drying then.Thereafter, calcine under the condition of 450 DEG C in atmosphere.And then, use paste 2 to repeat this screen painting and calcining, thus at SnO 2conducting film is formed the semi-conducting electrode (area of sensitive surface: 10mm × 10mm with the identical formation of semi-conducting electrode 42 shown in Fig. 2, thickness: 10 μm, the thickness of semiconductor layer: 6 μm, the thickness of light scattering layer: 4 μm, the bar-shaped TiO contained by light scattering layer 2the containing ratio of particle C: 30 quality %), make the optoelectronic pole of not containing metal complex compound pigment.
(pigment absorption)
Then, metal complex dye is made to be adsorbed on semi-conducting electrode (precursor of pigment adsorption electrode) as described below.First, using the mixture of 1: 1 (volume ratio) of anhydrous 3rd butanols that dewaters through ethoxyquin magnesium and dimethyl formamide as solvent, by the metal complex dye recorded in following table 4 to become 3 × 10 -4the mode of mol/L is dissolved, so add as coadsorbent relative to metal complex dye 1 mole be the chenodeoxycholic acid of 20 moles and cholic acid etc. molar mixture, prepare each pigment solution.Utilize Ka Er-Fischer (Karl-Fisher) titration to measure amount of moisture to this pigment solution, result water is less than 0.01 quality %.Then, semi-conducting electrode is flooded 10 hours at 40 DEG C in this solution, in addition dry at 50 DEG C after mentioning, be formed in absorption on semi-conducting electrode thus respectively and have an appointment 2 × 10 -7mol/cm 2the optoelectronic pole 40 of pigment.
(assembling of dye-sensitized solar cell)
Then, preparation is as the platinum electrode (thickness of Pt film: 100nm) with the shape identical with above-mentioned optoelectronic pole and size to electrode and the iodine system redox acetonitrile solution containing iodine 0.1M, lithium iodide 0.05M, 4-tributyl pyridine 0.25M as electrolyte.And then, prepare that there is the distance piece S (trade name: " sarin (Surlyn) ") manufactured with Du Pont (Dupont) company of the shape of the same size of semi-conducting electrode, make optoelectronic pole 40 relative with to electrode Jie CE compartment spacing body S and carry out thermo-compressed, above-mentioned electrolyte is filled in inside, use and long rapidsly change into resin XNR-5516 that (Nagase Chemitex) manufacture by the periphery of made battery and the sealing of electrolyte inlet and hardened, make each dye-sensitized solar cell (specimen coding 101 ~ specimen coding 136 respectively, specimen coding c11 ~ specimen coding c14).
As following, the performance of these each dye-sensitized solar cells is evaluated.
The evaluation > of < photoelectric conversion efficiency
Battery behavior test is that profit is carried out with the following methods: use solar simulator (Wa Kemu (WACOM) manufactures, WXS-85H), irradiate 1000W/m from the xenon lamp via AM 1.5 filter 2emulation sunlight.Use I-V tester to measure I-E characteristic, obtain photoelectric conversion efficiency.Relative to above-mentioned comparative compound (2), evaluate calculated photoelectric conversion efficiency by following benchmark.
A: be more than 1.5 times
B: be more than 1.1 times, be less than 1.5 times
B -: be greater than 1.0 times, be less than 1.1 times
C: be less than 1.0 times
Be shown in as conversion efficiency in following table 4.
The evaluation > of < heat deterioration
Made dye-sensitized solar cell is put into the thermostat of 40 DEG C and carry out heat resistant test.To the dye-sensitized solar cell before heat resistant test and heat resistant test, electric current evaluated by the dye-sensitized solar cell after 12 hours.Using the reduced value of the current value after heat resistant test divided by the value of the current value gained before heat resistant test as heat deterioration rate.Relative to above-mentioned comparative compound (2), evaluate the heat deterioration rate of gained like this by following benchmark.
A: be less than 0.9 times
B: be more than 0.9 times, be less than 1.0 times
C: be more than 1.0 times
Be shown in as heat deterioration in following table 4.
< thermal cycling test >
Every for made dye-sensitized solar cell 2 hours alternately put into the thermostat to the refrigerating chamber of-10 DEG C and 40 DEG C and repeatedly carry out cooling and heat, carrying out thermal cycling test.To the dye-sensitized solar cell before thermal cycling test and thermal cycling test, electric current evaluated by the dye-sensitized solar cell after 24 hours.Using the reduced value of the current value after heat resistant test divided by the value of the current value gained before thermal cycling test as deteriorated rate.Relative to above-mentioned comparative compound (1), evaluate by the deteriorated rate of following benchmark to gained like this.
A: be less than 0.9 times
B: be more than 0.9 times, be less than 1.0 times
C: be more than 1.0 times
Be shown in as thermal cycle in following table 4.
Moreover comparative compound (1) ~ comparative compound (4) is embodiment 2, the compound that uses in embodiment 3.
[table 4]
Specimen coding Metal complex dye Conversion efficiency Heat deterioration Thermal cycle Remarks
101 D-25 A B B The present invention
102 D-26 A A A The present invention
103 D-27 A A A The present invention
104 D-28 A A A The present invention
105 D-29 A A A The present invention
106 D-45 A A A The present invention
107 D-48 A A A The present invention
108 D-57 A B B The present invention
109 D-59 A A A The present invention
110 D-61 A A A The present invention
111 D-62 A A A The present invention
112 D-91 A A A The present invention
113 D-96 B A A The present invention
114 D-97 B A A The present invention
115 D-101 B A A The present invention
116 D-121 A A A The present invention
117 D-132 B B B The present invention
118 D-136 A A A The present invention
119 D-140 A A A The present invention
120 D-141 A A A The present invention
121 D-142 A A A The present invention
122 D-143 A A A The present invention
123 D-144 A A A The present invention
124 D-145 A A A The present invention
125 D-146 A A A The present invention
126 D-147 A A A The present invention
127 D-148 A A A The present invention
128 D-149 A A A The present invention
129 D-150 A A A The present invention
130 D-155 B B B The present invention
131 D-187 B A B The present invention
132 D-188 B A B The present invention
133 D-189 B B B The present invention
134 D-200 B A B The present invention
135 D-241 A A A The present invention
136 D-242 A A A The present invention
137 D-280 A B B The present invention
[continued 4]
Clearly learnt by above-mentioned table 4, use the dye-sensitized photoelectric conversion efficiency of the solar battery of the photo-electric conversion element made by metal complex dye of the present invention all high, and the durability confirmed by the deterioration of heat deterioration, thermal cycling test is all excellent.
Implement aspect to the present invention together with it to be illustrated in the lump, but can think, as long as the present inventor does not specify, then should not limit the invention to any detail section of explanation, and should explain widely when not violating spirit and the scope of the invention shown in the claims of enclosing.
The application advocates based on the Japan Patent Patent 2012-252700 of on November 16th, 2012 in Japan's proposition patent application, on November 16th, 2012 proposes the Japan Patent Patent 2012-252701 of patent application in Japan, on March 25th, 2013 proposes the Japan Patent Patent 2013-062895 of patent application in Japan, on June 19th, 2013 proposes the Japan Patent Patent 2013-129046 of patent application in Japan, on July 19th, 2013 proposes the Japan Patent Patent 2013-151149 of patent application in Japan, the priority proposing the Japan Patent Patent 2013-235218 of patent application in Japan in 13, on November of Japan Patent Patent 2013-205533 and 2013 of patent application is proposed in Japan on September 30th, 2013, with reference to these application cases its content is incorporated to herein as a part for the record of this specification.
The explanation of symbol
1: conductive support body
2: photoreceptor layers
21: pigment
22: semiconductor microactuator particle
3: Charger transfer body layer
4: to electrode
5: by optoelectronic pole
6: circuit
10: photo-electric conversion element
100: the system utilizing dye-sensitized solar cell
M: electro-motor (electric fan)
20: dye-sensitized solar cell
40: optoelectronic pole
41: transparency electrode
42: semi-conducting electrode
43: nesa coating
44: substrate
45: semiconductor layer
46: light scattering layer
CE: to electrode
E: electrolyte
S: distance piece

Claims (35)

1. a photo-electric conversion element, there is conductive support body, containing electrolytical photoreceptor layers, containing electrolytical Charger transfer body layer and to electrode, and described photoreceptor layers contains the semiconductor microactuator particle of the metal complex dye carried represented by following formula (I)
M (LA) (LD) (LX) mX(CI) mYformula (I)
[in formula, M represents metal ion;
LA represents the tridentate ligand represented by following formula (AL);
LD represents bidentate ligand or the tridentate ligand different from described LA; Herein, in described bidentate ligand or described tridentate ligand is anion with at least one of the coordination atom of metal ions M bond;
LX represents monodentate ligand; MX represents 1 when LD is bidentate ligand, represents 0 when LD is tridentate ligand;
CI represent must gegenion to make the gegenion during situation of charging neutrality;
MY represents the integer of 0 ~ 3];
[in formula, ring A, ring B and ring C separately represent nitrogenous heteroaromatic; Herein, Z 1and the key between atom N and Z 2and the key between atom N can be singly-bound and also can be double bond; Z 1and Z 2separately represent carbon atom or nitrogen-atoms;
Anc1 ~ Anc3 separately represents acidic groups; L1 and l3 separately represents the integer of 1 ~ 4, and l2 represents the integer of 1 ~ 5;
X 1and X 3separately represent singly-bound or concatenating group, X 2for with the X of at least one Anc2 institute bond of pi-conjugated link 2atom and the concatenating group of nitrogenous heteroaromatic of ring B or singly-bound, and when the situation for concatenating group in its coupling chain containing ethenylidene, ethynylene, arlydene or inferior heteroaryl; X 1with ring A, X 2with ring B, X 3also can bond and form contracting ring with ring C; M1 and m3 separately represents the integer of 0 ~ 4, and m2 represents the integer of 1 ~ 3; At X 2during situation for singly-bound, m1 or m3 represents the integer of 1 ~ 4, and X 1or X 3represent concatenating group;
R 1~ R 3separately represent the substituting group without Anc1 ~ Anc3; N1 and n2 separately represents the integer of 0 ~ 3, and n3 represents the integer of 0 ~ 4; At R 1~ R 3each when there is multiple situations respectively, they also can mutually bond and form ring].
2. photo-electric conversion element according to claim 1, wherein said M is Os 2+or Ru 2+.
3. photo-electric conversion element according to claim 1 and 2, wherein said X 2be separately any one or group that they are combined of singly-bound or following formula (X-1) ~ formula (X-6);
[in formula, Q 1represent and be selected from-S-,-O-,-N (R xA)-,-C (R xB) (R xC)-and-Si (R xB) (R xC)-in group; Herein, R xA~ R xCseparately represent hydrogen atom or substituting group; In addition, R xBwith R xCalso can bond and form ring mutually; R x1~ R x9separately represent hydrogen atom or substituting group; Herein, R x1with R x2, R x3with R x4, R x4with R x5, R x5with R xA, R x5with R xB, R x6with R x7, R x8with R x9respectively also can bond and form ring mutually; R x1~ R x4, R x6~ R x9also contracting ring can be formed with described ring B bond; * represent the binding site with described ring B, * * represents the binding site with described Anc2].
4. photo-electric conversion element according to any one of claim 1 to 3, wherein said X 1and described X 3at least one be separately any one or group that they are combined of following formula (X-1) ~ formula (X-6),
[in formula, Q 1represent and be selected from-S-,-O-,-N (R xA)-,-C (R xB) (R xC)-and-Si (R xB) (R xC)-in group; Herein, R xA~ R xCseparately represent hydrogen atom or substituting group; In addition, R xBwith R xCalso can bond and form ring mutually; R x1~ R x9separately represent hydrogen atom or substituting group; Herein, R x1with R x2, R x3with R x4, R x4with R x5, R x5with R xA, R x5with R xB, R x6with R x7, R x8with R x9respectively also can bond and form ring mutually; R x1~ R x4, R x6~ R x9also contracting ring can be formed with described ring A or ring C bond; * represent the binding site with described ring A or ring C, * * represents the binding site with described Anc1 or Anc3].
5. the photo-electric conversion element according to claim 3 or 4, the R of wherein said formula (X-1) x1with R x2be hydrogen atom.
6. the photo-electric conversion element according to claim 3 or 4, wherein said X 2for the group represented by described formula (X-1), described R x1or R x2for alkyl or aryl.
7. the photo-electric conversion element according to any one of Claims 1-4 and 6, wherein said X 2in pi-conjugated part-structure, have that=C (Rz)-("=" associative key is positioned at described ring B side to represented structure, and "-" associative key is positioned at described Anc2 side; Herein, Rz represents that the σ p value of Hammett's rule is the substituting group of more than 0.05).
8. the photo-electric conversion element according to any one of Claims 1-4 and 7, wherein said X 2represented by following formula (X-1A) or formula (X-2A),
[in formula, Rz represents that the σ p value of Hammett's rule is the substituting group of more than 0.05; Ring X represents aromatic carbon ring base or aromatic heterocycle; Herein, the associative key on the left of paper is binding on described ring B, and described Anc2 is binding on the associative key on the right side of paper].
9. photo-electric conversion element according to any one of claim 1 to 8, wherein said X 1and described X 3be separately described X 2represented concatenating group.
10. photo-electric conversion element according to any one of claim 1 to 9, wherein said ring B is pyridine ring.
11. photo-electric conversion elements according to any one of claim 1 to 10, wherein said ring A and described ring C is separately for being selected from the ring in pyridine ring, quinoline ring, pyrimidine ring, triazine ring, imidazole ring, benzimidazole Huan, oxazole ring, thiazole ring, benzothiazole Huan, oxadiazole rings, Thiadiazole, isoxazole ring, isothiazole ring, triazole ring and pyrazole ring.
12. photo-electric conversion elements according to any one of claim 1 to 11, wherein said ring A ~ described ring C is pyridine ring.
13. photo-electric conversion elements according to any one of claim 1 to 12, at least one of wherein said m1 and m3 is 1, and described m2 is 1.
14. photo-electric conversion elements according to any one of claim 1 to 13, wherein said m1 ~ m3 is 1.
15. photo-electric conversion elements according to any one of claim 1 to 8,10 to 14, wherein said m1 ~ described m3 is 1, and described X 2for singly-bound.
16. photo-electric conversion elements according to any one of claim 1 to 15, the bidentate ligand represented by any one that wherein said LD is following formula (2L-1) ~ formula (2L-5);
[in formula, ring D, " represent aromatic ring; A 111~ A 141separately represent nitrogen-atoms anion or carbon atom anion, A 151represent nitrogen-atoms anion, oxygen atom anion or sulphur atom anion; R 111~ R 154separately represent hydrogen atom or not there is the substituting group of Anc1, Anc2 and Anc3; Herein, * represents the binding site with described metal ions M].
17. photo-electric conversion elements according to any one of claim 1 to 15, the tridentate ligand represented by any one that wherein said LD is following formula (3L-1) ~ formula (3L-4),
[in formula, ring D, " represent aromatic ring; A 211~ A 242separately represent nitrogen-atoms or carbon atom; Wherein, each A 211with A 212, A 221with A 222, A 231with A 232, A 241with A 242at least one be anion; R 211~ R 241separately represent hydrogen atom or not there is the substituting group of Anc1, Anc2 and Anc3; Herein, * represents the binding site with described metal ions M].
18. photo-electric conversion elements according to any one of claim 1 to 17, the bidentate ligand of wherein said LD or the atom being coordinated in metal ions M of tridentate ligand are nitrogen anion or carboanion, and in part-structure, have following formula (SA),
[in formula, R dA1represent aryl, R dA2represent alkyl or aryl; R dA1with R dA2also can bond and form ring mutually; LL represents vinyl, acetenyl, arlydene or inferior heteroaryl; A represents the integer of 0 ~ 5].
19. photo-electric conversion elements according to any one of claim 1 to 18, wherein said formula (I) is represented by following formula (I-1) or formula (I-2),
[in formula, M and LX in M and LX and described formula (I) is synonymous, Anc1 ~ Anc3, X 1~ X 3, l1 ~ l3, m1 ~ m3, R 1~ R 3, Anc1 ~ Anc3, X in n1 ~ n3 and described formula (AL) 1~ X 3, l1 ~ l3, m1 ~ m3, R 1~ R 3, n1 ~ n3 is synonymous;
Ring D and ring E separately represents the aromatic ring of 5 rings or 6 rings; D 1and D 2separately represent hydrogen atom to dissociate and be binding on the carbon atom of M or hydrogen atom dissociates and is binding on the nitrogen-atoms of M; Herein, the D in ring D and ring E 1and D 2and with the key between the carbon atom of pyridine ring bond can be singly-bound and also can be double bond;
R a1~ R a4separately represent substituting group; Ma1, ma2 and ma4 separately represent the integer of 0 ~ 3; Ma3 represents the integer of 0 ~ 4;
When ma1 ~ ma4 is respectively the integer of more than 2, multiple R a1~ multiple R a4also can mutually bond and form ring].
20. photo-electric conversion elements according to claim 19, the ring D in wherein said formula (I-1) or formula (I-2) and ring E is separately pyrazole ring, triazole ring or phenyl ring.
21. photo-electric conversion elements according to any one of claim 1 to 20, wherein carry the coadsorbent with more than one acidic groups further on described semiconductor microactuator particle.
22. photo-electric conversion elements according to claim 21, wherein said coadsorbent is represented by following formula (CA),
[in formula, R a1represent the substituting group with acidic groups; R a2represent substituting group; NA represents the integer of more than 0].
23. 1 kinds of dye-sensitized solar cells, possess the photo-electric conversion element according to any one of claim 1 to 22.
24. 1 kinds of metal complex dyes, it is represented by following formula (I),
M (LA) (LD) (LX) mX(CI) mYformula (I)
[in formula, M represents metal ion;
LA represents the tridentate ligand represented by following formula (AL);
LD represents bidentate ligand or the tridentate ligand different from described LA; Herein, in described bidentate ligand or described tridentate ligand is anion with at least one of the coordination atom of metal ions M bond;
LX represents monodentate ligand; MX represents 1 when LD is bidentate ligand, represents 0 when LD is tridentate ligand;
CI represent must gegenion to make the gegenion during situation of charging neutrality;
MY represents the integer of 0 ~ 3];
[in formula, ring A, ring B and ring C separately represent nitrogenous heteroaromatic; Herein, Z 1and the key between atom N and Z 2and the key between atom N can be singly-bound and also can be double bond; Z 1and Z 2separately represent carbon atom or nitrogen-atoms;
Anc1 ~ Anc3 separately represents acidic groups; L1 and l3 separately represents the integer of 1 ~ 4, and l2 represents the integer of 1 ~ 5;
X 1and X 3separately represent singly-bound or concatenating group, X 2for with the X of at least one Anc2 institute bond of pi-conjugated link 2atom and the concatenating group of nitrogenous heteroaromatic of ring B or singly-bound, and when the situation for concatenating group in its coupling chain containing ethenylidene, ethynylene, arlydene or inferior heteroaryl; X 1with ring A, X 2with ring B, X 3also can bond and form contracting ring with ring C; M1 and m3 separately represents the integer of 0 ~ 4, and m2 represents the integer of 1 ~ 3; At X 2during situation for singly-bound, m1 or m3 represents the integer of 1 ~ 4, and X 1or X 3represent concatenating group;
R 1~ R 3separately represent the substituting group without Anc1 ~ Anc3; N1 and n2 separately represents the integer of 0 ~ 3, and n3 represents the integer of 0 ~ 4; At R 1~ R 3each when there is multiple situations respectively, they also can mutually bond and form ring].
25. metal complex dyes according to claim 24, wherein said X 2be separately any one or group that they are combined of singly-bound or following formula (X-1) ~ formula (X-6);
[in formula, Q 1represent and be selected from-S-,-O-,-N (R xA)-,-C (R xB) (R xC)-and-Si (R xB) (R xC)-in group; Herein, R xA~ R xCseparately represent hydrogen atom or substituting group; In addition, R xBwith R xCalso can bond and form ring mutually; R x1~ R x9separately represent hydrogen atom or substituting group; Herein, R x1with R x2, R x3with R x4, R x4with R x5, R x5with R xA, R x5with R xB, R x6with R x7, R x8with R x9respectively also can bond and form ring mutually; R x1~ R x4, R x6~ R x9also contracting ring can be formed with described ring B bond; * represent the binding site with described ring B, * * represents the binding site with described Anc2].
26. metal complex dyes according to claim 24 or 25, the bidentate ligand represented by any one that wherein said LD is following formula (2L-1) ~ formula (2L-5),
[in formula, ring D, " represent aromatic ring; A 111~ A 141separately represent nitrogen-atoms anion or carbon atom anion, A 151represent nitrogen-atoms anion, oxygen atom anion or sulphur atom anion; R 111~ R 154separately represent hydrogen atom or not there is the substituting group of Anc1, Anc2 and Anc3; Herein, * represents the binding site with described metal ions M].
27. ask the metal complex dye described in Entries 24 or 25 according to note before Please, the tridentate ligand represented by any one that wherein said LD is following formula (3L-1) ~ formula (3L-4),
[in formula, ring D, " represent aromatic ring; A 211~ A 242separately represent nitrogen-atoms or carbon atom; Wherein, each A 211with A 212, A 221with A 222, A 231with A 232, A 241with A 242at least one be anion; R 211~ R 241separately represent hydrogen atom or not there is the substituting group of Anc1, Anc2 and Anc3; Herein, * represents the binding site with described metal ions M].
28. metal complex dyes according to any one of claim 24 to 27, the bidentate ligand of wherein said LD or the atom being coordinated in metal ions M of tridentate ligand are nitrogen anion or carboanion, and there is following formula (SA) in part-structure
[in formula, R dA1represent aryl, R dA2represent alkyl or aryl; R dA1with R dA2also can bond and form ring mutually; LL represents vinyl, acetenyl, arlydene or inferior heteroaryl; A represents the integer of 0 ~ 5].
29. metal complex dyes according to any one of claim 24 to 28, wherein said X 2represented by following formula (X-1A) or formula (X-2A),
[in formula, Rz represents that the σ p value of Hammett's rule is the substituting group of more than 0.05; Ring X represents aromatic carbon ring base or aromatic heterocycle; Herein, the associative key on the left of paper is binding on described ring B, and described Anc2 is binding on the associative key on the right side of paper].
30. 1 kinds of pigment solutions, it is dissolved by the metal complex dye according to any one of claim 24 to 29 to form.
31. pigment solutions according to claim 30, it makes the described metal complex dye containing 0.001 quality % ~ 0.1 quality % in organic solvent, and is suppressed to be that below 0.1 quality % forms by water.
The pigment adsorption electrode of 32. 1 kinds of dye-sensitized solar cells, it is after giving the pigment solution having and the conductive support body of semiconductor microactuator particle is coated with according to claim 30 or 31, carries out reaction and hardens and make photoreceptor layers.
The manufacture method of 33. 1 kinds of dye-sensitized solar cells, it uses pigment adsorption electrode, electrolyte and each material to electrode becoming dye-sensitized solar cell according to claim 32 to assemble.
34. 1 kinds of compounds, it is represented by following formula (AL),
[in formula, ring A, ring B and ring C separately represent nitrogenous heteroaromatic; Herein, Z 1and the key between atom N and Z 2and the key between atom N can be singly-bound and also can be double bond; Z 1and Z 2separately represent carbon atom or nitrogen-atoms;
Anc1 ~ Anc3 separately represents acidic groups; L1 and l3 separately represents the integer of 1 ~ 4, and l2 represents the integer of 1 ~ 5;
X 1and X 3separately represent singly-bound or concatenating group, X 2for with the X of at least one Anc2 institute bond of pi-conjugated link 2atom and the concatenating group of nitrogenous heteroaromatic of ring B or singly-bound, and when the situation for concatenating group in its coupling chain containing ethenylidene, ethynylene, arlydene or inferior heteroaryl; X 1with ring A, X 2with ring B, X 3also can bond and form contracting ring with ring C; M1 and m3 separately represents the integer of 0 ~ 4, and m2 represents the integer of 1 ~ 3; At X 2during situation for singly-bound, m1 or m3 represents the integer of 1 ~ 4, and X 1or X 3represent concatenating group;
R 1~ R 3separately represent the substituting group without Anc1 ~ Anc3; N1 and n2 separately represents the integer of 0 ~ 3, and n3 represents the integer of 0 ~ 4; At R 1~ R 3each when there is multiple situations respectively, they also can mutually bond and form ring].
35. compounds according to claim 34, wherein said X 2for singly-bound, described m1 or m3 is the integer of 1 ~ 4, and described X 1or X 3for concatenating group.
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